research article synthesis of novel derivatives of...

Research ArticleSynthesis of Novel Derivatives of Carbazole-ThiopheneTheir Electronic Properties and Computational Studies

E F Damit1 N Nordin1 A Ariffin1 and K Sulaiman2

1Chemistry Department Science Faculty University of Malaya 50603 Kuala Lumpur Malaysia2Physic Department Science Faculty University of Malaya 50603 Kuala Lumpur Malaysia

Correspondence should be addressed to A Ariffin azhar70umedumy

Received 10 January 2016 Accepted 6 April 2016

Academic Editor Davut Avci

Copyright copy 2016 E F Damit et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

A series of carbazole-thiophene dimers P1ndashP9 were synthesized using Suzuki-Miyaura and Ullmann coupling reactions In P1ndashP9 carbazole-thiophenes were linked at the N-9 position for different core groups via biphenyl dimethylbiphenyl and phenylElectronic properties were evaluated by UV-Vis cyclic voltammogram and theoretical calculations Particularly the effects ofconjugation connectivity on photophysical and electrochemical properties as well as the correlation between carbazole-thiopheneand the core were studied Carbazole connecting with thiophenes at the 36-positions and the phenyl group as a core group leadsto increased stabilization of HOMO and LUMO energy levels where the bandgap (Δ119864) is significantly reduced

1 Introduction

Organic photovoltaics (OPVs) are alternatives to amorphoussilicon asmaterials for thin film solar cells Photovoltaics withsmall molecule-based active layers possess several potentialadvantages over polymer systems Compared to polymerssmall molecules do not suffer from the effects of polydisper-sity tend to have less batch-to-batch variation and are easilyfunctionalized and purified via standard techniques [1]120587-Conjugated oligomers and polymers have attracted

much attention in recent decades due to their potentialuses as semiconductors and electroactive materials in var-ious organic electronic devices such as organic field-effecttransistors (OFETs) organic light emitting diodes (OLEDs)organic solar cells (OSCs) and nonlinear optical devices [2ndash11]These oligomers have an advantage in terms of convenientfine-tuning of electronic photophysical and electrochemicalproperties by rational structuralmodification to achieve opti-mal device performance Moreover 120587-conjugated oligomerswith sophisticated functionalities are now key components inmolecular electronics [12 13]

Carbazole has fine optical properties a low redox poten-tial and high chemical stability thus oligopolycarbazoleshave served as representative benchmarkmaterials in OFETs

OLEDs and OSCs [14ndash18] Poly(36-carbazole)s and 36-functionalized carbazoles have been extensively studied overthe past few decades because carbazole groups can be easilyfunctionalized by electrophilic substitution at its 3- and 6-positions (para positions from the nitrogen atom) due toof their high electron density In this context carbazolescan be regarded as important scaffolds for the constructionof 120587-functional materials because of their rich diversityin structural modification Oligothiophenes particularly 120572-oligothiophenes are among the most intensively investigatedorganic compounds for a variety of materials applications[19 20] Hence mixed 120587-conjugated oligomers composedof carbazole and thiophene moieties have recently attractedconsiderable attention from the viewpoint of their potentialas the active component of organic electronics and theirsynthetic accessibility Various carbazole-thiophene hybridoligomers that are used as functional materials by using theirfluorescence and donor properties have been reported [21ndash25] in particular a large number of derivatives possessingthe anchoring and acceptor groups used for OSCs have beenrecently synthesized since the pioneering work by KoumuraHara and coworkers [26ndash32] However less attention hasbeen given to the clarification of the structure propertyrelationships in the carbazole-thiophene-based 120587-system

Hindawi Publishing CorporationJournal of ChemistryVolume 2016 Article ID 9360230 14 pageshttpdxdoiorg10115520169360230

2 Journal of Chemistry

which are indispensable for materials design Recently a largeseries of thienyl-substituted carbazole derivatives (thienylcar-bazoles) were synthesized and the effects of the connectionbetween the carbazole and thiophene moieties on the pho-tophysical and electrochemical properties were investigated[18] Studies have shown that both vapor and solution-baseddeposition of small molecules can lead to efficient multilayeror bulk heterojunction (BJH) devices suggesting the impor-tance of the final film microstructure rather than fabricationtechniques on device performance [33] Because themobilityof the charge carrier depends on the molecular orderingand hence the degree of crystallinity [34] small moleculesmay have the advantage of higher charge carrier mobilitiesDespite recent efforts to characterize themorphology of smallmolecule BHJs [35 36] knowledge regarding these systems isstill lacking In the current study a series of thienylcarbazoleswere prepared and detailed theoretical and experimentalinvestigation of the molecular planarity influenced by thedegree of conjunction at different types of cores and how thisproperty impacts 119864gap by investigating individual 119864LUMO and119864HOMO were carried out

Here the synthesis structural features and electronicand photophysical properties of P4ndashP9 (Figure 1) accordingto UV-Vis fluorescence spectroscopy cyclic voltammetryand theoretical calculations in comparison with reportedcompounds P1ndashP3 are described

2 Results and Discussion

21 Synthesis The synthesis of compounds P1ndashP9 wasdescribed in three parts as outlined in Schemes 1 and 2The key steps in the synthesis of the compounds involvedSuzuki-Miyaura [37] and Ullmann coupling [38] reactionsThe detailed procedures for the synthesis of the compoundare described in Section 4

The Ullmann coupling reaction was performed on car-bazole (1) with either 44-diiodobiphenyl (2) 44-diiodo-210158402-dimethyl-11-biphenyl (3) or 14-diiodobenzene (4) to giveP1 P2 and P3 in 50 60 and 80 yields respectivelyCompounds P1 (CBP) [39 40] P2 (CDBP) [41] and P3(BCP) [39 40] are known compounds

The syntheses of compounds P4 P5 and P6 wereachieved in three steps starting from carbazole (1) asdescribed in Scheme 1 The first step involved iodination of 1using 05 eq of iodine to give 3-iodocarbzole (5)This was fol-lowed by Suzuki-Miyaura cross coupling of 5with thiophene-2-boronic acid pinacol ester (6) to produce monothienyl-substituted carbazole (7) Ullmann coupling of compound 7with compounds 2 3 and 4 afforded compounds P4 P5 andP6 in 26 35 and 48 yields respectively

In a similar approach compounds P7 P8 and P9 weresynthesized in three steps from compound 1 as describedin Scheme 2 Iodination of compound 1 using 1 eq of iodinegave 36-diiodocarbazole (8) which was then refluxed withcompound 6 to give dithienyl-substituted carbazole (9)Ullmann coupling of 9 with 2 3 and 4 gave compounds P7P8 and P9 in 75 60 and 50 yields respectively Allof the compounds were fully characterized by spectroscopicmethods such as 1HNMR 13CNMR andmass spectroscopy

22 Electronic Absorption Spectroscopy The UV-Vis absorp-tion spectra of P1ndashP9 were measured in DMF solutions(Figures 3(a) 3(b) and 3(c)) and the 120582max

abs values forquantifying the extent of 120587-conjugation are summarized inTable 1 It is clearly observed from Figures 2(a)ndash2(c) that themaximum absorption peak shifts to a longer wavelength asthe number of thiophene groups increases The absorptionbands of all of the compounds were gradually red-shiftedwhen the thiophene group was connected to the carbazoleat the 3- and 6-positions and the extent of 120587-conjugation inthe compounds increased as expected Compounds P4 P5P6 P7 P8 and P9 show the longest wavelength absorptionsat 377 373 372 390 393 and 414 nm respectively (Figure 2)which were considerably red-shifted in comparison to thoseof compounds P1 P2 and P3 For compounds P7 P8 andP9 we noted a maximum absorption wavelength at a higherabsorbance indicating that the attachment of thiophenegroups at the 3- and 6-positions of the carbazolewith a phenylgroup core significantly enhances the optical properties(Figure 3(c)) Furthermore the slight shift of wavelength for afixed number of thiophene groups bridging biphenyl groupsdimethylbiphenyl and phenyl suggests that the differences incore groups in the compounds affect the optical propertiesNoticeably 120582max

abs are not affected by the changes of coregroups (Figures 3(a)ndash3(c))

It is well known that 120587-conjugated thiophene oligomersand polymers tend to 120587-stack because of the strong inter-molecular interaction between 120587-electrons [27] The differ-ence in intermolecular 120587-120587 interaction for these compoundswould account for the differences in the broadness of theirUV-Vis absorption spectra as shown in Figure 2 We alsoobserve that the broadness increased slightly as the numbersof thiophene groups increased [44]

It is well known that 120587-conjugated thiophene oligomersand polymers tend to 120587-stack due to the strong intermolec-ular interaction between 120587-electrons [27] The difference ofintermolecular 120587-120587 interaction for these compounds wouldaccount for their different broadness of UV-Vis absorptionspectra as shown in Figure 3 We also observe that thebroadness increased slightly with the increasing number ofthiophenes [44]

All the compounds P1ndashP9 are fluorescent After the func-tionalization of the carbazole groups the fluorescence max-ima (120582em) gradually red-shifted upon the addition of thio-phene group resulting in a significant red shift in the emis-sion spectrum as shown in Figures 4(a)ndash4(c) and the spectraldata are summarized in Table 1The broad absorption band inthe fluorescence spectra of P4P5P6P7P8 andP9 suggestthe contribution of a more rigid structure in the excited statenamely the quinoid state than the ground state [45] In con-trast to the absorption we note that the emission of P1 is red-shifted compared toP2 andP3 which is attributed to the pla-narization of P1 after the transition state to the excited stateSuch a geometric relaxation is not possible for P2 due to thebulkier side on the introduction ofmethyl group at core group(Figure 5(a)) [46] SimilarlyP4 is red-shifted compared toP5and P6 (Figure 5(b)) As the attachment of thiophene at 3-and 6- on the carbazole for P7 P8 and P9 120582em are not sig-nificantly affected by the change of core groups (Figure 5(c))

Journal of Chemistry 3

N N N N

NN

P1 P2

P3

N N

SS

N N

SS

P4 P5

N N

S

S

P6

N N

S

S

S

S

N N

S

S

S

S

P7 P8

NN

S

S

S

S

P9

Figure 1 Structures of compounds


1

HN

I

SB

O

OHN

S

(i) (ii)

(iii)

(iii)

(iii)

5

6

7

2

3

4

P4

P5

P6

I I

I I

I I

Scheme 1 Synthesis of P4P5 andP6 (i) I2(05 eq) AcOH and reflux (ii) K

2CO3 Pd(PPh

3)4 EtOH and reflux for 24 h (iii) K

2CO3 copper

powder 18-crown-6 o-DCB and reflux

1

HN

I

SB

O

O

HN

S8

6

9

2

3

4

P7

P8

P9

I

S

(i) (ii)

(iii)

(iii)

(iii)

Scheme 2 Synthesis of P7 P8 and P9 (i) I2(1 eq) AcOH and reflux (ii) K

2CO3 Pd(PPh


2CO3 Cu

18-crown-6 o-DCB and reflux

Table 1 UV-Vis spectroscopic data and fluorescence on 300 nmexcitationa

120582maxabs (nm) 120582onset (nm) 120582em

c (nm)P1 (CBP) 293 317b 340b 360 390P2 293 328b 341b 353 351P3 293 326b 340b 352 355P4 301 325b 377 413P5 293b 303 322b 373 396P6 294b 303 324b 372 394P7 318 344b 390 412P8 313 393 410P9 316 414 519aMeasured in DMF bPeak as shoulder cWavelength of the intensity maximaof the fluorescence at 300 nm excitation at room temperature

Carbazole-thiophenes possess nonplanar structures intheir ground state (119878

0) and become almost planar in the

lowest state (1198781) [47 48] This is expected because with the

addition of each thiophene group on P7 P8 and P9 thesecompounds are more conformationally flexible and thusproduce amore diffuse spectrum [49]The larger the numberof 120587-electrons in a chromophore the greater the shift to thered of the fluorescence and absorption spectra Thus thecharacteristics of a planar chromophore can be interpreted asbeing because in this configuration the number of functional120587-electrons is a maximum [50]

23 Electrochemical Properties To elucidate the effects of thedegree of conjugation between the core carbazole and thio-phene groups and the elongation of the molecular length ondonor ability and electrochemical stability cyclic voltamme-try (CV)was performed in a conventional three-electrode cellusing a platinum working electrode a platinum wire counterelectrode and a AgAgNO

3reference electrode In particular

the oxidation processes for P1ndashP9 were investigated in aDMF solution containing 005mol Lminus1 of n-Bu

4NPF6as a

supporting electrolyte (Figure 6) The oxidation potential

Journal of Chemistry 5N

orm

aliz

ed in

tens

ity (a

u)

00

02

04

06

08

10

12

290 310 330 350 370 390 410270Wavelength (nm)

P1P4P7

(a)

Nor

mal

ized

inte

nsity

(au

)

P2P5P8

290 310 330 350 370 390 410270Wavelength (nm)

00

02

04

06

08

10

12

(b)

Nor

mal

ized

inte

nsity

(au

)

P3P6P9

00

02

04

06

08

10

12

290 310 330 350 370 390 410 430270Wavelength (nm)

(c)

Figure 2 Electronic absorption spectra of (a) P1 P4 and P7 (b) P2 P5 and P8 and (c) P3 P6 and P9 recorded in DMF at 30∘C

Table 2 Oxidation potential (119864pa) and onset (119864onset) by cyclic voltammetry in DMF (005mol Lminus1 n-Bu4NPF6)a and optical HOMO-LUMO

gaps (Δ119864opt)b

119864pa (V) 119864onset (V) HOMOc (eV) LUMOd (eV) Δ119864optb (eV)

P1 +104 +089 minus569 minus563 [41] minus225 344 347 [41]P2 +113 +090 minus570 minus564 [41] minus218 352 351 [41]P3 +104 +082 minus562 minus209 353P4 +116 +090 minus570 minus241 329P5 +141 +109 minus589 minus256 333P6 +144 +114 minus594 minus260 334P7 +128 +092 minus572 minus254 318P8 +138 +105 minus585 minus269 316P9 +144 +119 minus599 minus299 300aAll potentials are given versus the Fc+Fc couple used as the external standard the scan rate is 100mV sminus1 bThe values are obtained from UVVis absorptiononset 120582onset

cThe values are those deduced from the 119864onset values according to the following equation HOMO = minus(48 + 119864onset) eV [42 43] dEstimated fromthe HOMO values and the optical band gap Δ119864opt

(119864pa) and onset (119864onset) versus Fc+Fc (ferroceniumferrocene

couple) are listed in Table 2Noticeably 119864pa values for P4ndashP9 (Figures 6(b) and 6(c))

are cathodically shifted compared to those for P1 P2 andP3 (Figure 6(a)) by the subsequent addition of thiophenemolecules demonstrating that the connection with thio-phene at the 3- and 6-positions of carbazole gives rise to

high electrochemical stability and effectively enhances donorability which should result from the effective resonancestabilization of the cationic species [51]

The HOMO levels of the compound were estimated fromthe half-wave potential of the first oxidation relative to theferrocene group As the reduction peaks are out of ourscan range the LUMO levels were calculated by adding the


00

02

04

06

08

10

12N

orm

aliz

ed in

tens

ity (a

u)

290 310 330 350 370 390 410270Wavelength (nm)

P1P2P3

(a)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410270Wavelength (nm)

P4P5P6

(b)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410 430270Wavelength (nm)

P7P8P9

(c)


optical bandgap to the HOMO levels Table 2 lists the valuesfor the HOMO and LUMO levels In the CV-experimentsthe subsequent introduction of thiophene groups at thecarbazole moieties in compounds P1 (CBP) P4 and P7causes decreases in the HOMO levels of minus569 minus570 andminus572 eV respectively In the case of methyl substitution onthe biphenyl ring in compounds P2 P5 and P8 the HOMOlevels decrease to minus570 minus589 and minus585 eV respectively incomparison with P1 P4 and P7 However by changing thebiphenyl core to phenyl rings for compounds P3 P6 and P9the HOMO levels are significantly affected (minus562 minus594 andminus599 eV resp)

TheHOMO levels of P6 andP9 are the lowest amongst allthe compounds indicating that the introduction of thiopheneand phenyl groups to the core leads to more stabilization ofHOMO energy levels [52] The order of the LUMO energiesis P3 gt P2 gt P1 gt P4 gt P7 gt P5 gt P6 gt P8 gt P9 indicatingthat compounds P8 and P9 possess greater electron-accept-ing abilities A lower LUMO level suggests stronger intra-molecular charge transfer interactions which result in a lowerbandgap (Figure 6) [53]

Δ119864 values decrease significantly with the change of thebridging core group from biphenyl to dimethylbiphenyl orphenyl in P1ndashP3 and P7ndashP9 whereas Δ119864 values in P4ndashP6increase in the presence of monothiophene at the 3-positionof carbazole The HOMO-LUMO gap of P9 is the narrowestamong these nine compounds which is expected to have themost outstanding photophysical properties Therefore thecarbazole substituted with thiophene groups at the 3- and 6-positions and phenyl as the core group leads to greater stabili-zation ofHOMOandLUMOenergy levelswhere the bandgap(Δ119864) of all of the compounds is significantly reduced

These considerations show that the energy levels of theCBP derivatives can be fine-tuned to some extent by varyingthe substitution pattern at the connecting biphenyl moietyas well as at the pendant carbazole Particularly the HOMOlevels can be varied Thus through these slight variationsin the molecular structure the energy of the different lay-ers in optoelectronic devices can be adjusted to minimizeenergy barriers within the devices [41] 120587-Functional smallmolecules benefit from the fact that they are easy to purifytend to possess high intrinsic carrier mobilities and are able


00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P4P7

(a)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P2P5P8

(b)

0001020304050607080910

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P3P6P9

(c)

Figure 4 Emission spectra of (a) P1 P4 and P7 (b) P2 P5 and P8 and (c) P3 P6 and P9 recorded in DMF at 30∘C

to self-assemble to achieve long-range order An impressivelibrary of thiophene oligomers has been built and exploredover the past two decades [54 55] Symmetrical donor-acceptor (DA) small molecules appended with solubilizingsubstituents and consisting of an electron-deficient coreflanked with electron-rich groups are now being consideredas alternatives to their all-donor counterparts [56]

24 Theoretical Approach To obtain further insight into theelectronic properties of P1ndashP9 geometrical optimization andfrontiermolecular orbital calculations were performed All ofthe computationswere performedusing theGAUSSIAN09Wsoftware package (Tables S1ndashS9 in Supplementary Materialavailable online at httpdxdoiorg10115520169360230)The images presented in the figures were generated usingChemDraw and GaussView visualization programs Thegeometries of the compounds in their ground state were opti-mized (Figure 6) employing the Density Functional Theory(DFT)methodwith restricted Beckersquos three parameter hybridfunctional and the nonlocal Lee Yang and Parr gradient-corrected correlation functional B3LYP [57 58] combinedwith the 6-31G functional basis set This method has beenfound to be an accurate formalism for calculating the char-acteristic parameters of many molecular systems [59]

The contour plots of the HOMO and LUMO determinedat the DFTB3LYP6-31G level for all of the compoundsare shown in Figure 7 The HOMO is expected to lieon the electron-rich groups affording an effective hole-transporting property The energy of the HOMO and LUMOorbitals is an important molecularly correlated parameterThe molecules with lower HOMO orbital energy levels haveweaker electron-donating abilities Moreover the electronicdensity distribution in these orbitals permits prediction ofthe most probable sites of attack by reactive agents in themolecules investigated

From the HOMO and LUMO orbitals shown in Figure 7the HOMO is predominantly determined by the carbazolegroups for P1ndashP3 whereas for P4ndashP7 the HOMO aremainly determined by the thiophene groups and their 120587-bonding orbitals although the carbazoles also exert theirinfluence however the LUMOs are predominantly localizedon and primarily determined by the carbazole and biphenylcore groups and their 120587lowast-bonding orbitals CompoundsP8 and P9 demonstrate an overlap between HOMO andLUMO on the acceptor carbazole group which facilitatesthe charge transfer from the four electron-donating thio-phene groups to the two electron-withdrawing carbazoles[53] In addition to the stronger electron-donating ability


00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)


of the thiophene compounds P7 P8 and P9 exhibit moreplanar structures and more effective 120587-conjugation whichresult in strengthened intramolecular interactions and lowerbandgaps These results are consistent with the experimen-tally observed absorption properties of the resulting com-pound (Figure 3(c)) A clear difference between biphenyl anddimethylbiphenyl as core groups can be observed

In fact for N-carbazole end-capped-120587-conjugatedmolecules the introduction of carbazole moieties at theterminal group of the conjugated backbone would result in aless planar molecule due to the planar character of carbazolegroupsThis fact is manifested by a perpendicular orientationto the backbone chain which decreases the bond lengthbetween the core and the carbazole group This decrease isattributed to the size and the electronegativity of the nitrogenatomThese large dihedral angles could minimize the degreeof 120587-aggregation and thus improve the photoluminescenceintensity [52] Particularly the 36-disubstituted structurespresent high dipole moments indicating the presence of asignificant charge transfer This effect is more pronounced inthe case of D-A structures (P4ndashP9) [52]

3 Conclusion

In conclusion a series of carbazole-thiophene derivativesP4ndashP9 were prepared by means of Suzuki-Miyaura andUllmann coupling reactions as key steps The electronicstructures were determined by UV-Vis fluorescence spectralmeasurements CV and theoretical calculations Based onthis study a clear picture about the effects of the structuralvariations of carbazole-thiophenes the degree of conjugationand the insertion of different core groups on their electronicand electrochemical properties emerges The connection ofcarbazole-thiophene with a phenyl core and the additionof thiophene groups at the 3- and 6-positions resulted in acomposite structure that exhibited a red shift in the emissionspectrum Carbazole connecting with more thiophenes and aphenyl core group leads to greater stabilization of the HOMOand LUMO energy levels where the bandgap (Δ119864) of allof the compound-based-compounds is significantly reducedThe present study provides valuable information for thedesign and synthesis of new carbazole-thiophene-based sys-tems


P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)

02 04 06 08 10 12 14 1600Potential (V versus AgAg+)

(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)

05 10 15 2000Potential (V versus AgAg+)

(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)

Figure 6 Cyclic voltammogram (01 Vsminus1) for (a) compounds P1 P2 and P3 (b) compounds P4 P5 and P6 and (c) compounds P7 P8and P9 with ferrocene as an external standard in DMFmdash005M nBu

4NPF6

4 Experimental Section

41 General Information All chemicals were commerciallyavailable and used as received unless otherwise specified1H NMR (400 and 600MHz) and 13C NMR (100MHz)spectra were recorded using a spectrometer Chemical shiftsare reported in parts per million (ppm) relative to theresidual solvent protons (1H) or the solvent carbon (13C)as internal standards The mass spectra and high-resolutionmass spectra (HRMS)were obtained using either electrosprayionization (ESI) atmospheric pressure chemical ionization(APCI) techniques or MALDI-Tof Absorption spectra wererecorded on a UV-Vis spectrometer Cyclic voltammetry(CV) was carried out using working electrode as glassycarbon and counter electrode was platinum electrodes andAgAg+ (010M AgNO

3in DMF) as reference electrode

The electrochemical potential was calibrated against FcFc+Theoretical Density Functional Theory (DFT) calculationwas performed using GAUSSIAN 09W software packageusing the B3LYP method and 6-31G basis set

42 Synthesis of Compounds

421 Preparation of Compound P1ndashP9 General proce-dure of Ullmann coupling procedure for preparation ofcarbazole-thiophene is as follows A mixture of carbazole1 3-(thiophen-2-yl)carbazole 7 or 36-(dithiophene-2-yl)9H-carbazole 9 (2 eq) and 44-diiodobiphenyl 2 44-diiodo-210158402-dimethyl-11-biphenyl 3 or 14-diiodobenzene 4 (1 eq) in 12-dichlorobenzene (10mL) was purged with nitrogen for 30minutes K

2CO3(1 eq) copper powder (2 eq) and 18-crown-

6 (20mol) were added to the mixture and the resultingmixture was refluxed under nitrogen atmosphere for 3 daysThe organic phase was filtered and the solvent removed undervacuo and purified with column chromatography (silicaethyl acetate-hexane) to afford desired products

422 Preparation of Compounds 7 and 9 General procedurefor the Suzuki-Miyaura cross-coupling procedure for thepreparation of carbazole-thiophene is as follows A mixtureof 3-iodocarbazole 5 or 36-diiodocarbazole 8 (1 eq) dissolved


HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9

Figure 7 HOMO and LUMO frontier molecular orbitals of compounds P1ndashP9 that were calculated in vacuo at B3LYP6-31G level ofapproximation


in 80mL absolute ethanol was treated with a few drops ofTHFuntil themixture completely dissolved and thiophene-2-boronic acid pinacol ester6was added to the solution K

2CO3

(2 eq) in ethanolwater (10 1) was then added and purgedwith nitrogen for 30min Pd(PPh

3)4(ca 05ndash1 per reaction

point) was added to the mixture and the resulting mixturewas refluxed under a nitrogen atmosphereThe organic phasewas separated and the aqueous phase was extracted withdichloromethaneThe combined organic phases were washedwith water dried over Na

2SO4 and concentrated under

reduce pressure Recrystallization from hexane-dichloro-methane afforded the desired product

423 44-Diiodobiphenyl (2) [60] A mixture of biphenyl4 (462 g 30mmol) acetic acid 30mL water 3mL con-centrated sulfuric acid 3mL iodine 837 g periodic acid(375 g 165mmol) and carbon tetrachloride (CCl

4 4mL)

was stirred and maintained at 80∘C for 4 hours Afterwardsthe slurry product was cooled to room temperature pouredinto water and extracted with dichloromethane The com-bined dark purple organic layer was decolorized with sodiumsulfite dried with anhydrous sodium sulfate filtered andevaporated to dryness yielding 399 g of 2 pale yellow shinypowder (33) mp 200ndash202∘C (mplit 200-201∘C) 1H NMR(400MHz CDCl

3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730

(d 119869 = 856Hz 4 H) 13C NMR (100MHz CDCl3) 120575

1396 1377 1287 935 HR-ESI-MS 119898119911 calcd for [M +H]+ = C

12H8I24068795 found 4068793 Anal calcd for

C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243

424 441015840-Di(9H-carbazol-9-yl)-111015840-biphenyl (P1) [41] Thetitle compound was prepared from 2 eq carbazole 1 (009 g050mmol) and 1 eq 44-diiodobiphenyl 2 (010 g 025mmol)as white shiny powder P1 (007 g 50) Mp 283 1H NMR(400MHz CDCl

3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795

(d 119869 = 844Hz 4 H) 774 (d 119869 = 856Hz 4 H) 755 (d119869 = 790Hz 4 H) 748 (td 119869 = 710 100Hz 4 H) 735 (td119869 = 680 100Hz 4 H) 13C NMR (100MHz CDCl

3) 120575 ppm

1408 1393 1373 1285 1275 1260 1235 1204 1201 1098HR-ESI-MS 119898119911 calcd for [M + H]+ = C

36H24N24852017

found 4852015 Anal calcd for C36H24N2 C 8923 H 499

N 578 Found C 8920 H 480 N 572

425 991015840-(221015840-Dimethyl-[111015840-biphenyl]-441015840-diyl)bis(9H-car-bazole) (P2) [41] The title compound was prepared from22 eq of carbazole 1 (017 g 005mmol) and 1 eq of 44-diiodo-210158402-dimethyl-11-biphenyl 3 (010 g 002mmol) Pur-ification by column chromatography (silica dichlorometh-ane-hexane) gave P2 as a white powder (001 g 60) 1HNMR (400MHz CDCl

3) 120575 ppm 821 (d 119869 = 770Hz 4 H)

755ndash760 (m 6 H) 745ndash755 (m 8 H) 735 (td 119869 = 740098Hz 4 H) 232 (s 6 H) 13C NMR (100MHz CDCl

3)

120575 ppm 1409 1400 1379 1369 1308 1283 1259 1243 12341203 1199 1099 2013 HR-ESI-MS 119898119911 calcd for [M +H]+ = C

38H28N25132330 found 5132332 Anal calcd for

C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543

426 14-Di(9H-carbazol-9-yl)benzene (P3) The title com-pound was prepared from 2 eq of carbazole 1 (008 g050mmol) and 1 eq of 14-diiodobenzene 4 (010 g023mmol) Purification by column chromatography(silica dichloromethane-hexane) gave P3 as a white solid(008 g 80) Mp 323∘C 1HNMR (400MHz CDCl

3) 120575 ppm

822 (d 119869 = 758Hz 4 H) 785 (s 4 H) 760 (d 119869 = 820Hz 4H) 751 (td 119869 = 767 116Hz 4 H) 737 (td 119869 = 740 098Hz4 H) 13C NMR (100MHz CDCl

3) 120575 ppm 1408 1369 1284

1261 1236 1204 1203 1097 HR-ESI-MS119898119911 calcd for [M+ H]+ = C

30H20N24091704 found 4091706 Anal calcd

for C30H20N2 C 8821 H 493 N 686 Found C 8818 H

490 N 679

427 3-Iodocarbazole (5) [61] Carbazole 1 (167 g 101mmol)was dissolved in boiling glacial acetic acid (250mL) andKI (1173 g 135mmol) was added The solution was cooledground potassium iodate (2342 g 150mmol) was addedand the mixture was boiled until it acquired a clear straw-colored tint (10min)The hot solution was decanted from theundissolved potassium iodate and it was allowed to cool to45∘C The faintly brown plates were rapidly filtered off andrecrystallized from alcohol and the solution was allowed tocool to 45∘CThe faintly brown plates were rapidly filtered offand recrystallized from ethanol the solution was allowed tocool to 45∘C and filtered yielding 973 g (47) of 5 as a brownsolid mp 202∘C (mplit 202∘C) 1H NMR (600MHz CDCl

3)

120575 ppm 841 (s 1 H) 811 (br s 1 H) 804 (d 119869 = 770Hz1 H) 768 (dd 119869 = 853 174Hz 1 H) 742ndash749 (m 2 H)722ndash728 (m 2 H) 13CNMR (100MHz CDCl

3) 120575 ppm 1395

1386 1341 1292 1266 1259 1221 1205 1199 1126 1107Maldi-TofMS119898119911 calcd for [M+] = C

12H8IN 292970 found

292971 Anal calcd for C12H8IN C 4917 H 275 I 4330

N 478 Found C 4910 H 271 I 4325 N 473

428 3-(Thiophen-2-yl)carbazole (7) [62] The title productwas prepared from 3-iodocarbazole 5 (24 g 80mmol) as anoff-white solid (160 g 80) mp 196∘C mplit 197∘C 1HNMR(600MHz CDCl

3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1

H) 810 (br s 1 H) 772 (d 119869 = 834Hz 1 H) 742ndash750 (m4 H) 737 (d 119869 = 348Hz 1 H) 729ndash733 (m 1 H) 713 (ddd119869 = 502 355 142Hz 1 H) 13C NMR (100MHz CDCl

3) 120575

1457 1400 1390 1280 1264 1262 1246 1238 1237 12331222 1205 1197 1179 1109 1108 HR-ESI-MS119898119911 calcd for[M+H]+ =C

16H11NS 2500692 found 2500690 Anal calcd

for C16H11NS C 7711 H 445 N 562 S 1283 Found C

7708 H 440 N 558 S 1279

429 Preparation of P4 The compound was preparedfrom 2 eq of 3-(thiophene-2-yl)-9H-carbazole 7 (03241 g13mmol) and 1 eq of 44-diiodobiphenyl 2 (025 g 06mmol)as an off-white solid (01 g 26) 1HNMR(400MHzCDCl

3)

120575 ppm 841 (s 2 H) 824 (d 119869 = 831Hz 2 H) 797 (d119869 = 807Hz 4 H) 775 (dd 119869 = 862 312Hz 6 H) 750ndash758(m 5 H) 733ndash743 (m 5 H) 731 (d 119869 = 477Hz 2 H) 715 (t119869 = 420Hz 2 H) 13C NMR (100MHz CDCl

3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101


HR-ESI-MS119898119911 calcd for [M +H]+ =C44H28N2S26491772

found 6491775 Anal calcd forC44H28N2S2 C 8147H 435

N 432 S 986 Found C 8145 H 432 N 428 S 982

4210 Preparation of P5 The compound was preparedfrom 2 eq of 3-(thiophene-2-yl)-9H-carbazole 7 (012 g048mmol) and 1 eq of 44-diiodo-210158402-dimethyl-11-biphenyl3 (010 g 023mmol) as a pale yellow solid (005 g 35) 1HNMR (400MHz CDCl

3) 120575 ppm 842 (s 2 H) 824 (d 119869 =

746Hz 2 H) 775 (d 119869 = 856Hz 2 H) 746ndash760 (m 12 H)741 (dd 119869 = 355 110Hz 2 H) 736 (td 119869 = 743 092Hz 2H) 731 (dd 119869 = 514 110Hz 2 H) 716 (dd 119869 = 514 355Hz2 H) 233 (s 6 H) 13CNMR (100MHz CDCl

3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101202 HR-ESI-MS 119898119911 calcd for [M + H]+ = C

46H32N2S2

6772085 found 6772080 Anal calcd for C46H32N2S2 C

8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941

4211 Preparation of P6 The compound was preparedfrom 2 eq of 3-(thiophene-2-yl)-9H-carbazole 7 (016 g060mmol) and 1 eq of 14-diiodobenzene 4 (010 g030mmol) Purification by column chromatography (silicachloroform-hexane) gave P6 as a pale yellow solid (008 g48) 1H NMR (600MHz CDCl

3) 120575 ppm 842 (s 2 H) 825

(d 119869 = 752Hz 2 H) 787 (s 4 H) 777 (dd 119869 = 853 174Hz2 H) 760 (t 119869 = 860Hz 4 H) 752 (td 119869 = 750 100Hz 2H) 742 (dd 119869 = 348 110Hz 2 H) 739 (t 119869 = 697Hz 2 H)732 (dd 119869 = 504 101Hz 2 H) 716 (dd 119869 = 514 348Hz2 H) 13C NMR (100MHz CDCl

3) 120575 ppm 1283 1281 1272

1265 1248 1241 1240 1235 1224 1206 1206 1180 11011099 HR-ESI-MS 119898119911 calcd for [M + H]+ = C

38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113

4212 36-Diiodocarbazole (8) [61] Carbazole 1 (1223 g73mmol) was dissolved in boiling glacial acetic acid(300mL) and KI (1584 g 95mmol) was addedThe solutionwas cooled ground potassium iodate (2342 g 150mmol) wasadded and the mixture was then boiled until it acquireda clear straw-colored tint (10min) The hot solution wasdecanted from the undissolved potassium iodate and it wasallowed to cool to 45∘CThe faintly brown plates were rapidlyfiltered off and recrystallized from alcohol and the solutionwas allowed to cool to 45∘C and filtered yielding 575 g of 8as a brown solid (1879) mp 202∘C (mplit 202∘C) 1HNMR(400MHz CDCl

3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770

(dd 119869 = 853 163Hz 2 H) 723 (d 119869 = 841Hz 2 H) 13CNMR (100MHz CDCl

3) 120575 1385 1348 1294 1245 1127 and

825 Maldi-Tof MS119898119911 calcd for [M+] = C12H7I2N 418867

found 418868 Anal calcd for C12H7I2N C 3440 H 168 I

6058 N 334 Found C 3438 H 165 I 6055 N 330

4213 36-Di(thiophen-2-yl)-9H-carbazole (9) The com-pound was prepared from 36-diiodocarbazole 8 as a whitesolid (070 g 59) mp 127∘C 1H NMR (600MHz CDCl

3)

120575 ppm835 (s 2H) 813 (br s 1 H) 773 (dd 119869 = 839 170Hz2 H) 744 (d 119869 = 853Hz 2 H) 738 (d 119869 = 348Hz 2 H)730 (d 119869 = 504Hz 2 H) 723 (dd 119869 = 1036 853Hz 1H) 712ndash716 (m 2 H) 13C NMR (100MHz CDCl

3) 120575 1455

1394 1280 1267 1249 1239 1238 1223 1180 1111 HR-ESI-MS 119898119911 calcd for [M + H]+ = C

20H13NS23320569 found

3320569 Anal calcd for C20H13NS2 C 7252 H 395 N

423 S 1930 Found C 7249 H 391 N 419 S 1927

4214 Preparation of P7 The compound was preparedfrom 2 eq of 36-di(thiophen-2-yl)-9H-carbazole 9 (043 g130mmol) and 1 eq of 44-diiodobiphenyl 2 (025 g060mmol) Recrystallization from absolute ethanol gaveP7 as a pale yellow solid (10 g 75) 1H NMR (600MHzCDCl

3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776

(d 119869 = 807Hz 8 H) 753 (d 119869 = 844Hz 4 H) 743 (dd119869 = 348 110Hz 4 H) 732 (dd 119869 = 513 092Hz 4 H) 716(dd 119869 = 495 348Hz 5 H) 13C NMR (100MHz CDCl

3)

120575 ppm 1453 1408 1394 1370 1287 1281 1273 1273 12501240 1239 1225 1180 1104 Mp 268∘C HR-APCI-MS119898119911calcd for [M + H]+ = C

52H32N2S48131526 found 8131522

Anal calcd for C52H32N2S4 C 7685 H 397 N 345 S

1574 Found C 7682 H 395 N 341 S 1570

4215 Preparation of P8 The compound was preparedfrom 22 eq of 36-di(thiophen-2-yl)-9H-carbazole 9 (017 g005mmol) and 1 eq of 44-diiodo-210158402-dimethyl-11-biphenyl3 (010 g 002mmol) Purification by column chromatogra-phy (silica dichloromethane-hexane) gaveP8 as a white solid(001 g 60) 1H NMR (400MHz CDCl

3) 120575 ppm 845 (s 4

H) 769ndash783 (m 6 H) 749ndash763 (m 6 H) 737ndash749 (m 6 H)729ndash735 (m 4 H) 711ndash719 (m 4 H) 128 (s 6 H) 13C NMR(100MHz CDCl

3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518

4216 Preparation of P9 The compound was prepared from2 eq of 36-di(thiophen-2-yl)-9H-carbazole 9 (021 g060mmol) and 1 eq of 14-diiodobenzene 4 (010 g030mmol) Purification by column chromatography (silicachloroform-hexane) gave P9 as a pale yellow solid (01 g50) 1H NMR (400MHz CDCl

3) 120575 ppm 846 (s 4 H) 790

(s 4 H) 779 (dd 119869 = 850 165Hz 4 H) 760 (d 119869 = 844Hz4 H) 744 (d 119869 = 355Hz 4 H) 733 (d 119869 = 452Hz 4H) 717 (dd 119869 = 495 361Hz 4 H) 13C NMR (100MHzCDCl

3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251

1241 1240 1226 1181 1103 HR-ESI-MS 119898119911 calcd for [M+ H]+ = C

46H28N2S47371213 found 7371210 Anal calcd

for C46H28N2S4 C 7501 H 383 N 380 S 1736 Found C

7499 H 380 N 377 S 1732

Competing Interests

The authors declare no competing financial interests


Acknowledgments

The authors are thankful for the support of the Chem-istry Department Faculty of Science University MalayaKuala Lumpur Malaysia and for financial support from theLong Term Research Grant Scheme (LRGS) (LR003-2011A)High Impact Research Grant (HIR) (UMC6251HIR208)(J-21001-73865) and Postgraduate Research Grant (PPP)(PG021-2013A)

References

[1] AMishra and P Bauerle ldquoSmall molecule organic semiconduc-tors on the move promises for future solar energy technologyrdquoAngewandte Chemie International Edition vol 51 no 9 pp2020ndash2067 2012

[2] H Klauk Organic Electronics Materials Manufacturing andApplications John Wiley amp Sons New York NY USA 2006

[3] K Mullen and U Scherf Eds Organic Light Emitting DevicesSynthesis Properties and Applications Wiley-VCH WeinheimGermany 2006

[4] T J J Muller and U H F Bunz Functional Organic MaterialsSyntheses Strategies and Applications Wiley-VCH WeinheimGermany 2007

[5] ZHKafafiOrganic Electroluminescence CRCPressNewYorkNY USA 2005

[6] M M Haley and R R Tykwinski Carbon-Rich CompoundsfromMolecules to Materials JohnWiley amp Sons New York NYUSA 2006

[7] T W Kelley P F Baude C Gerlach et al ldquoRecent progress inorganic electronics materials devices and processesrdquo Chem-istry of Materials vol 16 no 23 pp 4413ndash4422 2004

[8] S R Forrest and M E Thompson ldquoIntroduction organicelectronics and optoelectronicsrdquo Chemical Reviews vol 107 no4 pp 923ndash925 2007

[9] M Bendikov F Wudl and D F Perepichka ldquoTetrathiaful-valenes oligoacenenes and their buckminsterfullerene deriva-tives the brick and mortar of organic electronicsrdquo ChemicalReviews vol 104 no 11 pp 4891ndash4945 2004

[10] Y Shirota and H Kageyama ldquoCharge carrier transportingmolecularmaterials and their applications in devicesrdquoChemicalReviews vol 107 no 4 pp 953ndash1010 2007

[11] WWu Y Liu andD Zhu ldquo120587-Conjugatedmolecules with fusedrings for organic field-effect transistors design synthesis andapplicationsrdquo Chemical Society Reviews vol 39 no 5 pp 1489ndash1502 2010

[12] N J Tao ldquoElectron transport in molecular junctionsrdquo Naturenanotechnology vol 1 no 3 pp 173ndash181 2006

[13] J C Cuevas and E Scheer Molecular Electronics An Introduc-tion to Theory and Experiment vol 1 World Scientific RiverEdge NJ USA 2010

[14] J V Grazulevicius P Strohriegl J Pielichowski and K Pieli-chowski ldquoCarbazole-containing polymers synthesis propertiesand applicationsrdquo Progress in Polymer Science vol 28 no 9 pp1297ndash1353 2003

[15] J-F Morin M Leclere D Ades and A Siove ldquoPolycarbazoles25 years of progressrdquo Macromolecular Rapid Communicationsvol 26 no 10 pp 761ndash778 2005

[16] N Blouin and M Leclerc ldquoPoly(27-carbazole)s structure-property relationshipsrdquo Accounts of Chemical Research vol 41no 9 pp 1110ndash1119 2008

[17] P L T Boudreault J F Morin and M Leclerc ldquoSynthesis ofpoly(27-carbazole)s and derivativesrdquo inDesign and Synthesis ofConjugated Polymers pp 205ndash226 2010

[18] S-I Kato H Noguchi A Kobayashi T Yoshihara S Tobitaand Y Nakamura ldquoBicarbazoles systematic structure-propertyinvestigations on a series of conjugated carbazole dimersrdquoJournal ofOrganic Chemistry vol 77 no 20 pp 9120ndash9133 2012

[19] A Mishra C-Q Ma and P Bauerle ldquoFunctional oligothio-phenes molecular design for multidimensional nanoarchitec-tures and their applicationsrdquo Chemical Reviews vol 109 no 3pp 1141ndash1176 2009

[20] I F Perepichka and D F Perepichka Handbook of Thiophene-BasedMaterials Applications inOrganic Electronics and Photon-ics Wiley Online Library 2009

[21] J-F Morin N Drolet Y Tao and M Leclerc ldquoSynthesesand characterization of electroactive and photoactive 27-carba-zolenevinylene-based conjugated oligomers and polymersrdquoChemistry of Materials vol 16 no 23 pp 4619ndash4626 2004

[22] M Belletete J-F Morin M Leclerc and G Durocher ldquoAtheoretical spectroscopic and photophysical study of 27-carbazolenevinylene-based conjugated derivativesrdquoThe Journalof Physical Chemistry A vol 109 no 31 pp 6953ndash6959 2005

[23] J Lu P F Xia P K Lo Y Tao and M S Wong ldquoSynthesis andproperties of multi-triarylamme-substituted carbazole-baseddendrimers with an oligothiophene core for potential applica-tions in organic solar cells and light-emitting diodesrdquoChemistryof Materials vol 18 no 26 pp 6194ndash6203 2006

[24] M Melucci L Favaretto C Bettini et al ldquoLiquid-crystallinerigid-core semiconductor oligothiophenes influence of molec-ular structure on phase behaviour and thin-film propertiesrdquoChemistrymdashA European Journal vol 13 no 36 pp 10046ndash10054 2007

[25] T Khanasa N Prachumrak R Rattanawan et al ldquoBis(carbazol-9-ylphenyl) aniline end-capped oligoarylenes as solution-processed nondoped emitters for full-emission color tuningorganic light-emitting diodesrdquo The Journal of Organic Chem-istry vol 78 no 13 pp 6702ndash6713 2013

[26] N Koumura Z-S Wang S Mori M Miyashita E Suzukiand K Hara ldquoAlkyl-functionalized organic dyes for efficientmolecular photovoltaicsrdquo Journal of the American ChemicalSociety vol 128 no 44 pp 14256ndash14257 2006

[27] Z-S Wang N Koumura Y Cui et al ldquoHexylthiophene-func-tionalized carbazole dyes for efficient molecular photovoltaicstuning of solar-cell performance by structural modificationrdquoChemistry of Materials vol 20 no 12 pp 3993ndash4003 2008

[28] N Koumura Z-S Wang M Miyashita et al ldquoSubstituted car-bazole dyes for efficient molecular photovoltaics long electronlifetime and high open circuit voltage performancerdquo Journal ofMaterials Chemistry vol 19 no 27 pp 4829ndash4836 2009

[29] Y Ooyama Y Shimada S Inoue et al ldquoNew molecular designof donor-120587-acceptor dyes for dye-sensitized solar cells controlof molecular orientation and arrangement on TiO

2surfacerdquo

New Journal of Chemistry vol 35 no 1 pp 111ndash118 2011[30] W Lee N Cho J Kwon J Ko and J-I Hong ldquoNew organic dye

based on a 36-disubstituted carbazole donor for efficient dye-sensitized solar cellsrdquo ChemistrymdashAn Asian Journal vol 7 no2 pp 343ndash350 2012

[31] C Chen J-Y Liao Z Chi et al ldquoMetal-free organic dyesderived from triphenylethylene for dye-sensitized solar cellstuning of the performance by phenothiazine and carbazolerdquoJournal of Materials Chemistry vol 22 no 18 pp 8994ndash90052012


[32] T Sudyoadsuk S Pansay S Morada et al ldquoSynthesis and char-acterization of DndashDndash120587ndashA-type organic dyes bearing carbazole-carbazole as a donor moiety (DndashD) for efficient dye-sensitizedsolar cellsrdquo European Journal of Organic Chemistry vol 2013no 23 pp 5051ndash5063 2013

[33] G Wei R R Lunt K Sun S Wang M EThompson and S RForrest ldquoEfficient ordered bulk heterojunction nanocrystallinesolar cells by annealing of ultrathin squaraine thin filmsrdquo NanoLetters vol 10 no 9 pp 3555ndash3559 2010

[34] V Coropceanu J Cornil D A da Silva Filho Y Olivier RSilbey and J-L Bredas ldquoCharge transport in organic semicon-ductorsrdquo Chemical Reviews vol 107 no 4 pp 926ndash952 2007

[35] B Walker A B Tamayo X-D Dang et al ldquoNanoscalephase separation and high photovoltaic efficiency in solution-processed small-molecule bulk heterojunction solar cellsrdquoAdvanced Functional Materials vol 19 no 19 pp 3063ndash30692009

[36] BWalker C Kim and T-Q Nguyen ldquoSmallmolecule solution-processed bulk heterojunction solar cellsrdquo Chemistry of Materi-als vol 23 no 3 pp 470ndash482 2011

[37] NMiyaura andA Suzuki ldquoPalladium-catalyzed cross-couplingreactions of organoboron compoundsrdquo Chemical Reviews vol95 no 7 pp 2457ndash2483 1995

[38] I P Beletskaya and A V Cheprakov ldquoCopper in cross-couplingreactions the post-Ullmann chemistryrdquo Coordination Chem-istry Reviews vol 248 no 21ndash24 pp 2337ndash2364 2004

[39] B R Kaafarani A O El-Ballouli R Trattnig et al ldquoBis(carba-zolyl) derivatives of pyrene and tetrahydropyrene synthesisstructures optical properties electrochemistry and electrolu-minescencerdquo Journal of Materials Chemistry C vol 1 no 8 pp1638ndash1650 2013

[40] B E Koene D E Loy and M E Thompson ldquoAsymmetrictriaryldiamines as thermally stable hole transporting layers fororganic light-emitting devicesrdquo Chemistry of Materials vol 10no 8 pp 2235ndash2250 1998

[41] P Schrogel A Tomkeviciene P Strohriegl S T HoffmannA Kohler and C Lennartz ldquoA series of CBP-derivatives ashost materials for blue phosphorescent organic light-emittingdiodesrdquo Journal of Materials Chemistry vol 21 no 7 pp 2266ndash2273 2011

[42] C Chi and G Wegner ldquoChain-length dependence of the elec-trochemical properties of conjugated oligofluorenesrdquo Macro-molecular Rapid Communications vol 26 no 19 pp 1532ndash15372005

[43] J PommerehneHVestweberWGuss et al ldquoEfficient two layerLEDs on a polymer blend basisrdquo Advanced Materials vol 7 no6 pp 551ndash554 1995

[44] K Hara K Miyamoto Y Abe and M Yanagida ldquoElectrontransport in coumarin-dye-sensitized nanocrystalline TiO

2

electrodesrdquoThe Journal of Physical Chemistry B vol 109 no 50pp 23776ndash23778 2005

[45] H Cao J Ma G Zhang and Y Jiang ldquoBorolethiophene cooli-gomers and copolymers with quinoid structures and biradicalcharactersrdquoMacromolecules vol 38 no 4 pp 1123ndash1130 2005

[46] S T Hoffmann P Schrogel M Rothmann R Q AlbuquerqueP Strohriegl and A Kohler ldquoTriplet excimer emission in aseries of 441015840-bis(N-carbazolyl)-221015840-biphenyl derivativesrdquo TheJournal of Physical Chemistry B vol 115 no 3 pp 414ndash421 2011

[47] M Belletete M Bedard M Leclerc and G Durocher ldquoGroundand excited state properties of carbazole-based dyads correla-tion with their respective absorption and fluorescence spectrardquo

Journal of Molecular Structure THEOCHEM vol 679 no 1-2pp 9ndash15 2004

[48] L Yang J-K Feng A-M Ren and J-Z Sun ldquoThe electronicstructure and optical properties of carbazole-based conjugatedoligomers and polymers a theoretical investigationrdquo Polymervol 47 no 4 pp 1397ndash1404 2006

[49] K R Radke K Ogawa and S C Rasmussen ldquoHighly fluo-rescent oligothiophenes through the incorporation of centraldithieno[3 2-b 21015840 31015840-d]pyrrole unitsrdquo Organic Letters vol 7no 23 pp 5253ndash5256 2005

[50] I B Berlman ldquoEmpirical correlation between nuclear confor-mation and certain fluorescence and absorption characteristicsof aromatic compoundsrdquoThe Journal of Physical Chemistry vol74 no 16 pp 3085ndash3093 1970

[51] S-I Kato S Shimizu A Kobayashi T Yoshihara S Tobita andY Nakamura ldquoSystematic structurendashproperty investigations ona series of alternating carbazolendashthiophene oligomersrdquo TheJournal of Organic Chemistry vol 79 no 2 pp 618ndash629 2014

[52] A Hlel A Mabrouk M Chemek I Ben Khalifa and KAlimi ldquoA DFT study of charge-transfer and opto-electronicproperties of some new materials involving carbazole unitsrdquoComputational Condensed Matter vol 3 pp 30ndash40 2015

[53] X Lu S Fan J Wu X Jia Z-S Wang and G Zhou ldquoCon-trolling the charge transfer in D-A-D chromophores based onpyrazine derivativesrdquoThe Journal of Organic Chemistry vol 79no 14 pp 6480ndash6489 2014

[54] A R Murphy and J M J Frechet ldquoOrganic semiconductingoligomers for use in thin film transistorsrdquo Chemical Reviewsvol 107 no 4 pp 1066ndash1096 2007

[55] S Allard M Forster B Souharce H Thiem and U ScherfldquoOrganic semiconductors for solutionminusprocessable fieldminuseffecttransistors (OFETs)rdquo Angewandte ChemiemdashInternational Edi-tion vol 47 no 22 pp 4070ndash4098 2008

[56] P M Beaujuge and J M J Frechet ldquoMolecular design andordering effects in 120587-functional materials for transistor andsolar cell applicationsrdquo Journal of the American ChemicalSociety vol 133 no 50 pp 20009ndash20029 2011

[57] N Acar J Kurzawa N Fritz et al ldquoPhenothiazinemdashpyrenedyads photoinduced charge separation and structural relax-ation in the CT staterdquo Journal of Physical Chemistry A vol 107no 45 pp 9530ndash9541 2003

[58] C Lee W Yang and R G Parr ldquoDevelopment of the Colle-Salvetti correlation-energy formula into a functional of theelectron densityrdquo Physical Review B vol 37 no 2 pp 785ndash7891988

[59] S Tretiak and S Mukamel ldquoDensity matrix analysis and sim-ulation of electronic excitations in conjugated and aggregatedmoleculesrdquo Chemical Reviews vol 102 no 9 pp 3171ndash32122002

[60] Y Wu H Guo T D James and J Zhao ldquoEnantioselectiverecognition of mandelic acid by a 36-dithiophen-2-yl-9H-carbazole-based chiral fluorescent bisboronic acid sensorrdquo TheJournal of Organic Chemistry vol 76 no 14 pp 5685ndash56952011

[61] S H Tucker ldquoIodination in the carbazole seriesrdquo Journal of theChemical Society vol 1 pp 548ndash553 1926

[62] D Kim J K Lee S O Kang and J Ko ldquoMolecular engineeringof organic dyes containing N-aryl carbazole moiety for solarcellrdquo Tetrahedron vol 63 no 9 pp 1913ndash1922 2007

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

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Advances in

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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


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Medicinal ChemistryInternational Journal of


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Applied ChemistryJournal of



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CatalystsJournal of


which are indispensable for materials design Recently a largeseries of thienyl-substituted carbazole derivatives (thienylcar-bazoles) were synthesized and the effects of the connectionbetween the carbazole and thiophene moieties on the pho-tophysical and electrochemical properties were investigated[18] Studies have shown that both vapor and solution-baseddeposition of small molecules can lead to efficient multilayeror bulk heterojunction (BJH) devices suggesting the impor-tance of the final film microstructure rather than fabricationtechniques on device performance [33] Because themobilityof the charge carrier depends on the molecular orderingand hence the degree of crystallinity [34] small moleculesmay have the advantage of higher charge carrier mobilitiesDespite recent efforts to characterize themorphology of smallmolecule BHJs [35 36] knowledge regarding these systems isstill lacking In the current study a series of thienylcarbazoleswere prepared and detailed theoretical and experimentalinvestigation of the molecular planarity influenced by thedegree of conjunction at different types of cores and how thisproperty impacts 119864gap by investigating individual 119864LUMO and119864HOMO were carried out

Here the synthesis structural features and electronicand photophysical properties of P4ndashP9 (Figure 1) accordingto UV-Vis fluorescence spectroscopy cyclic voltammetryand theoretical calculations in comparison with reportedcompounds P1ndashP3 are described

2 Results and Discussion

21 Synthesis The synthesis of compounds P1ndashP9 wasdescribed in three parts as outlined in Schemes 1 and 2The key steps in the synthesis of the compounds involvedSuzuki-Miyaura [37] and Ullmann coupling [38] reactionsThe detailed procedures for the synthesis of the compoundare described in Section 4

The Ullmann coupling reaction was performed on car-bazole (1) with either 44-diiodobiphenyl (2) 44-diiodo-210158402-dimethyl-11-biphenyl (3) or 14-diiodobenzene (4) to giveP1 P2 and P3 in 50 60 and 80 yields respectivelyCompounds P1 (CBP) [39 40] P2 (CDBP) [41] and P3(BCP) [39 40] are known compounds

The syntheses of compounds P4 P5 and P6 wereachieved in three steps starting from carbazole (1) asdescribed in Scheme 1 The first step involved iodination of 1using 05 eq of iodine to give 3-iodocarbzole (5)This was fol-lowed by Suzuki-Miyaura cross coupling of 5with thiophene-2-boronic acid pinacol ester (6) to produce monothienyl-substituted carbazole (7) Ullmann coupling of compound 7with compounds 2 3 and 4 afforded compounds P4 P5 andP6 in 26 35 and 48 yields respectively

In a similar approach compounds P7 P8 and P9 weresynthesized in three steps from compound 1 as describedin Scheme 2 Iodination of compound 1 using 1 eq of iodinegave 36-diiodocarbazole (8) which was then refluxed withcompound 6 to give dithienyl-substituted carbazole (9)Ullmann coupling of 9 with 2 3 and 4 gave compounds P7P8 and P9 in 75 60 and 50 yields respectively Allof the compounds were fully characterized by spectroscopicmethods such as 1HNMR 13CNMR andmass spectroscopy

22 Electronic Absorption Spectroscopy The UV-Vis absorp-tion spectra of P1ndashP9 were measured in DMF solutions(Figures 3(a) 3(b) and 3(c)) and the 120582max

abs values forquantifying the extent of 120587-conjugation are summarized inTable 1 It is clearly observed from Figures 2(a)ndash2(c) that themaximum absorption peak shifts to a longer wavelength asthe number of thiophene groups increases The absorptionbands of all of the compounds were gradually red-shiftedwhen the thiophene group was connected to the carbazoleat the 3- and 6-positions and the extent of 120587-conjugation inthe compounds increased as expected Compounds P4 P5P6 P7 P8 and P9 show the longest wavelength absorptionsat 377 373 372 390 393 and 414 nm respectively (Figure 2)which were considerably red-shifted in comparison to thoseof compounds P1 P2 and P3 For compounds P7 P8 andP9 we noted a maximum absorption wavelength at a higherabsorbance indicating that the attachment of thiophenegroups at the 3- and 6-positions of the carbazolewith a phenylgroup core significantly enhances the optical properties(Figure 3(c)) Furthermore the slight shift of wavelength for afixed number of thiophene groups bridging biphenyl groupsdimethylbiphenyl and phenyl suggests that the differences incore groups in the compounds affect the optical propertiesNoticeably 120582max

abs are not affected by the changes of coregroups (Figures 3(a)ndash3(c))

It is well known that 120587-conjugated thiophene oligomersand polymers tend to 120587-stack because of the strong inter-molecular interaction between 120587-electrons [27] The differ-ence in intermolecular 120587-120587 interaction for these compoundswould account for the differences in the broadness of theirUV-Vis absorption spectra as shown in Figure 2 We alsoobserve that the broadness increased slightly as the numbersof thiophene groups increased [44]

It is well known that 120587-conjugated thiophene oligomersand polymers tend to 120587-stack due to the strong intermolec-ular interaction between 120587-electrons [27] The difference ofintermolecular 120587-120587 interaction for these compounds wouldaccount for their different broadness of UV-Vis absorptionspectra as shown in Figure 3 We also observe that thebroadness increased slightly with the increasing number ofthiophenes [44]

All the compounds P1ndashP9 are fluorescent After the func-tionalization of the carbazole groups the fluorescence max-ima (120582em) gradually red-shifted upon the addition of thio-phene group resulting in a significant red shift in the emis-sion spectrum as shown in Figures 4(a)ndash4(c) and the spectraldata are summarized in Table 1The broad absorption band inthe fluorescence spectra of P4P5P6P7P8 andP9 suggestthe contribution of a more rigid structure in the excited statenamely the quinoid state than the ground state [45] In con-trast to the absorption we note that the emission of P1 is red-shifted compared toP2 andP3 which is attributed to the pla-narization of P1 after the transition state to the excited stateSuch a geometric relaxation is not possible for P2 due to thebulkier side on the introduction ofmethyl group at core group(Figure 5(a)) [46] SimilarlyP4 is red-shifted compared toP5and P6 (Figure 5(b)) As the attachment of thiophene at 3-and 6- on the carbazole for P7 P8 and P9 120582em are not sig-nificantly affected by the change of core groups (Figure 5(c))


N N N N

NN

P1 P2

P3

N N

SS

N N

SS

P4 P5

N N

S

S

P6

N N

S

S

S

S

N N

S

S

S

S

P7 P8

NN

S

S

S

S

P9



1

HN

I

SB

O

OHN

S

(i) (ii)

(iii)

(iii)

(iii)

5

6

7

2

3

4

P4

P5

P6

I I

I I

I I


2CO3 Pd(PPh


2CO3 copper


1

HN

I

SB

O

O

HN

S8

6

9

2

3

4

P7

P8

P9

I

S

(i) (ii)

(iii)

(iii)

(iii)


2CO3 Pd(PPh


2CO3 Cu












4NPF6as a



orm

aliz

ed in

tens

ity (a

u)

00

02

04

06

08

10

12

290 310 330 350 370 390 410270Wavelength (nm)

P1P4P7

(a)

Nor

mal

ized

inte

nsity

(au

)

P2P5P8

290 310 330 350 370 390 410270Wavelength (nm)

00

02

04

06

08

10

12

(b)

Nor

mal

ized

inte

nsity

(au

)

P3P6P9

00

02

04

06

08

10

12

290 310 330 350 370 390 410 430270Wavelength (nm)

(c)



gaps (Δ119864opt)b










00

02

04

06

08

10

12N

orm

aliz

ed in

tens

ity (a

u)

290 310 330 350 370 390 410270Wavelength (nm)

P1P2P3

(a)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410270Wavelength (nm)

P4P5P6

(b)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410 430270Wavelength (nm)

P7P8P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P4P7

(a)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P2P5P8

(b)

0001020304050607080910

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P3P6P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)




3 Conclusion



P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N N N N

NN

P1 P2

P3

N N

SS

N N

SS

P4 P5

N N

S

S

P6

N N

S

S

S

S

N N

S

S

S

S

P7 P8

NN

S

S

S

S

P9



1

HN

I

SB

O

OHN

S

(i) (ii)

(iii)

(iii)

(iii)

5

6

7

2

3

4

P4

P5

P6

I I

I I

I I


2CO3 Pd(PPh


2CO3 copper


1

HN

I

SB

O

O

HN

S8

6

9

2

3

4

P7

P8

P9

I

S

(i) (ii)

(iii)

(iii)

(iii)


2CO3 Pd(PPh


2CO3 Cu












4NPF6as a



orm

aliz

ed in

tens

ity (a

u)

00

02

04

06

08

10

12

290 310 330 350 370 390 410270Wavelength (nm)

P1P4P7

(a)

Nor

mal

ized

inte

nsity

(au

)

P2P5P8

290 310 330 350 370 390 410270Wavelength (nm)

00

02

04

06

08

10

12

(b)

Nor

mal

ized

inte

nsity

(au

)

P3P6P9

00

02

04

06

08

10

12

290 310 330 350 370 390 410 430270Wavelength (nm)

(c)



gaps (Δ119864opt)b










00

02

04

06

08

10

12N

orm

aliz

ed in

tens

ity (a

u)

290 310 330 350 370 390 410270Wavelength (nm)

P1P2P3

(a)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410270Wavelength (nm)

P4P5P6

(b)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410 430270Wavelength (nm)

P7P8P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P4P7

(a)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P2P5P8

(b)

0001020304050607080910

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P3P6P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)




3 Conclusion



P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


1

HN

I

SB

O

OHN

S

(i) (ii)

(iii)

(iii)

(iii)

5

6

7

2

3

4

P4

P5

P6

I I

I I

I I


2CO3 Pd(PPh


2CO3 copper


1

HN

I

SB

O

O

HN

S8

6

9

2

3

4

P7

P8

P9

I

S

(i) (ii)

(iii)

(iii)

(iii)


2CO3 Pd(PPh


2CO3 Cu












4NPF6as a



orm

aliz

ed in

tens

ity (a

u)

00

02

04

06

08

10

12

290 310 330 350 370 390 410270Wavelength (nm)

P1P4P7

(a)

Nor

mal

ized

inte

nsity

(au

)

P2P5P8

290 310 330 350 370 390 410270Wavelength (nm)

00

02

04

06

08

10

12

(b)

Nor

mal

ized

inte

nsity

(au

)

P3P6P9

00

02

04

06

08

10

12

290 310 330 350 370 390 410 430270Wavelength (nm)

(c)



gaps (Δ119864opt)b










00

02

04

06

08

10

12N

orm

aliz

ed in

tens

ity (a

u)

290 310 330 350 370 390 410270Wavelength (nm)

P1P2P3

(a)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410270Wavelength (nm)

P4P5P6

(b)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410 430270Wavelength (nm)

P7P8P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P4P7

(a)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P2P5P8

(b)

0001020304050607080910

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P3P6P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)




3 Conclusion



P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


orm

aliz

ed in

tens

ity (a

u)

00

02

04

06

08

10

12

290 310 330 350 370 390 410270Wavelength (nm)

P1P4P7

(a)

Nor

mal

ized

inte

nsity

(au

)

P2P5P8

290 310 330 350 370 390 410270Wavelength (nm)

00

02

04

06

08

10

12

(b)

Nor

mal

ized

inte

nsity

(au

)

P3P6P9

00

02

04

06

08

10

12

290 310 330 350 370 390 410 430270Wavelength (nm)

(c)



gaps (Δ119864opt)b










00

02

04

06

08

10

12N

orm

aliz

ed in

tens

ity (a

u)

290 310 330 350 370 390 410270Wavelength (nm)

P1P2P3

(a)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410270Wavelength (nm)

P4P5P6

(b)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410 430270Wavelength (nm)

P7P8P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P4P7

(a)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P2P5P8

(b)

0001020304050607080910

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P3P6P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)




3 Conclusion



P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


00

02

04

06

08

10

12N

orm

aliz

ed in

tens

ity (a

u)

290 310 330 350 370 390 410270Wavelength (nm)

P1P2P3

(a)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410270Wavelength (nm)

P4P5P6

(b)

00

02

04

06

08

10

12

Nor

mal

ized

inte

nsity

(au

)

290 310 330 350 370 390 410 430270Wavelength (nm)

P7P8P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P4P7

(a)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P2P5P8

(b)

0001020304050607080910

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P3P6P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)




3 Conclusion



P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P4P7

(a)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P2P5P8

(b)

0001020304050607080910

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

P3P6P9

(c)







00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)




3 Conclusion



P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


00

02

04

06

08

10N

orm

aliz

ed in

tens

ity (a

u)

350 400 450 500 550 600300Wavelength (nm)

P1P2P3

(a)

P4P5P6

350 400 450 500 550 600300Wavelength (nm)

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

(b)

P7P8P9

00

02

04

06

08

10

Nor

mal

ized

inte

nsity

(au

)

350 400 450 500 550 600300Wavelength (nm)

(c)




3 Conclusion



P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


P1P2P3

minus01

01

03

05

07

09

11

13N

orm

aliz

ed cu

rren

t (m

A)


(a)

P4P5P6

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(b)

P7P8P9

minus01

01

03

05

07

09

11

13

Nor

mal

ized

curr

ent (

mA

)


(c)


4NPF6











HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


HOMO LUMO

P1 (CBP)

P2

P3

P4

P5

P6

P7

P8

P9




2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



2CO3







4 4mL)


3) 120575 ppm 778 (d 119869 = 856Hz 4 H) 730




C12H8I2 C 3550 H 199 I 6251 Found C 3545 H 180 I

6243


3) 120575 ppm 821 (d 119869 = 770Hz 4 H) 795


3) 120575 ppm


36H24N24852017


N 578 Found C 8920 H 480 N 572


3) 120575 ppm 821 (d 119869 = 770Hz 4 H)


3)



C38H28N2 C 8903 H 550 N 546 Found C 8900 H 545

N 543


3) 120575 ppm


3) 120575 ppm 1408 1369 1284




490 N 679


3)


3) 120575 ppm 1395


12H8IN 292970 found


N 478 Found C 4910 H 271 I 4325 N 473


3) 120575 ppm 832 (s 1 H) 814 (d 119869 = 779Hz 1


3) 120575




7708 H 440 N 558 S 1279


3)


3) 120575 ppm 1456

1414 1404 1401 1380 1367 1308 1283 1280 1268 12631246 1242 1239 1233 1223 1205 1202 1179 1103 1101




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




N 432 S 986 Found C 8145 H 432 N 428 S 982


3) 120575 ppm 842 (s 2 H) 824 (d 119869 =


3) 120575 ppm 1456


46H32N2S2


8165 H 477 N 414 S 945 Found C 8162 H 474 N410 S 941


3) 120575 ppm 842 (s 2 H) 825


3) 120575 ppm 1283 1281 1272


38H24N2S2


7972 H 422 N 489 S 1117 Found C 7969 H 420 N486 S 1113


3) 120575 ppm 834 (s 2 H) 816 (br s 1 H) 770


3) 120575 1385 1348 1294 1245 1127 and



6058 N 334 Found C 3438 H 165 I 6055 N 330


3)


3) 120575 1455


20H13NS23320569 found


423 S 1930 Found C 7249 H 391 N 419 S 1927


3) 120575 ppm 844 (s 4 H) 798 (d 119869 = 844Hz 3 H) 776


3)


52H32N2S48131526 found 8131522


1574 Found C 7682 H 395 N 341 S 1570


3) 120575 ppm 845 (s 4


3) 120575 ppm 1456 1454 1421 1418 1409 1281


54H36N2S4


7714 H 432 N 333 S 1521 Found C 7712 H 430 N329 S 1518


3) 120575 ppm 846 (s 4 H) 790


3) 120575 ppm 1452 1406 1295 1283 1281 1275 1251




7499 H 380 N 377 S 1732

Competing Interests



Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Acknowledgments


References






























2surfacerdquo


















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of















2






























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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