Victor Furer

Molecular structure and IR spectra of phosphorus dendrimers by DFT calculations

Kazan State Architect and Civil Engineering University

2

Scheme of dendrimer synthesis

Divergent

Convergent

A. Juris, Annu. Rep. Prog. Chem., Sect. C, 2003, 99, 177

3

1

1

NNB

G

BCNBC

MNNNMNMMW G

BB

G

BRUCC 1

1

NNZ G

BCNumber of terminal groups

Number of repeated units

Molecular mass

Topology of dendrimers

4N. Launay et al, Angew. Chem., Int. Ed. Engl. 1994, 33, 1589

Structural scheme of growing denrimer generations

Core Number of repeated unit Number of terminal groups

Generation Molecular mass P

S

H-C-O

CH3

- =N-N-

P

S

P

S

H-C-O

O-

(-Сl)

G’0 (G 0) 426 (168) 1 - - - 3 G’1 (G1) 1423 (903) 1 3 - 3 6 G’2 (G2) 417 (2389) 1 9 3 6 12 G’3 (G3) 7405 5349) 1 21 9 12 24

G’4 15381 1 45 21 24 48 G’5 31332 1 93 45 48 96 G’6 63234 1 189 93 96 192 G’7 127038 1 381 189 192 384 G’8 254647 1 765 381 384 768 G’9 509866 1 1533 765 768 1536

G’10 1020301 1 3069 1533 1536 3072 G’11 2041175 1 6141 3069 3072 6144

Note: in parents presented data for the series with terminal chlorine atoms.

Composition and mass of molecules of 11 generations of phosphorus

dendrimers, series G’i (Gi)

5

P

S

Core H-C-O

CH 3

- =N-N- P

S

Repeated unit H-C-O

O-Terminal group

IR spectra of series G’i phosphorus dendrimers

6

IR spectra of series Gi phosphorus dendrimers

P

S

Core H-C-O

CH 3

- =N-N- P

S

Repeated unit Terminal group -Cl

7

Raman spectra of series G’i phosphorus dendrimers

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1640 1620 1600 1580 1560 1540 1520 1500 1480

G'2

G 3

Пог

лощ

ение

, см-1

Comparison of IR spectra series Gi и G’i

9

8а 19а

1600 см-1 1500 см-1

1800 1600 1400 1200 1000 800 600 4000

1

2

3

4

,см-1

4

3

2

1

Пог

лощ

ение

1600 1400 1200 1000 800 600 4000

1

2

3

4

1

2

3

4

,см-1

Пог

лощ

ение

MeMeMe

OSP

O

MeMeMe- C=N

OCH3

PN

SO

HO

n

MeMeMe

HC

O

- Cl2

Calculated absorption curves for the chain with number of units n = 1 (1), n = 11 (3) and

experimental IR spectra of dendrimers G’1 (2) and G’11 (4).

Calculated absorption curves for the chain with number of units n = 2 (1), n = 3 (3) and

experimental IR spectra of dendrimers G2 (2) and G3 (4).

IR spectra, theoretical curves and model fragments(approximation of linear chains)

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L.A.Gribov, Theory of IR spectra of polymers, М.: Nauka, 1977.

1800 1600 1400 1200 1000 800 600 400

0

1

2

,см-1

2

1

Пог

лощ

ение

1800 1600 1400 1200 1000 800 600 400

0,0

0,5

1,0

1,5

2,0

, см-1

2

1

Пог

лощ

ение

O HO

S

N P3CH

OMeMeMe

MeMeMeMeMeMe

NC=- O HO

S

N P3CH

OMeMeMe NC=-

Cl

Cl

fragment II fragment IIIfragment I

Sum of theoretical absorption curves for the fragments I and II (1) and

experimental IR spectra of generation G’5 (2).

Sum of theoretical absorption curves for the fragmentsI and III (1) and

experimental IR spectra of generation G3 (2).

IR spectra, theoretical curves and model fragments(fragment approximation)

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Experimental IR spectra, theoretical curves (DFT)

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PRIRODAFunctional PBE

Базис TZ2PD. Laikov, Chem. Phys. Lett., 1997, 281, 151

M.-L.Lartigue et al, Macromolecules, 1997, 30, 7335

1600 1400 1200 1000 800 600 400

G'0

exp. cryst.

exp. melt

calc

Wavenumber,cm-1

1600 1400 1200 1000 800 600 400

G1

exp.

calc.

Wavenumber, cm-1

R

T T

C

RRRR

TTT

T R R T

T

R TT

R RR

RT

T

TT

R

RT T

RT

T R

R

RRT

TT T

RR

TT

R=c(rn-1)/(r-1) T=crn (G0) С=1, R=0, T=c

(G1) С=1, R=c, T=cr

(G2) С=1, R=c(r+1), T=cr2 G0= С+3Т and G1= С+3R+3Т

G1 - G0 =C+3R+6T–2(C+3T) =3R–C

G2-G1=С+9R+12T–2(C+3R+6T)=3R–C

G3-G2 =C+21R+24T-2(C+9R+12T)=3R-C

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Theory of spectral «additivity»

Experimental IR spectra of generation G2 and the difference IR spectra (G3 – G2)

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1600 1400 1200 1000 800 600 400

G2

G3

G2

Wavenumber,cm-1

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Experimental IR spectra of generation G’2 and the difference IR spectra (G’3 – G’2)

and (G’11 – G’10)

1800 1600 1400 1200 1000 800 600

G'10

G'11

G'2

G'3

G'2

Wavenumber,cm-1

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The difference Raman spectra

1800 1600 1400 1200 1000 800 600 400

G'2

G'8

G'10

G'6

G'8

G'4

G'6

G'2

G'4

G'0

Wavenumber,cm-1

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Experimental IR spectra of generations G3, G’2 and the difference IR spectra (G’2 – G3)

1800 1600 1400 1200 1000 800 600 400

G3

G'2

G3

G'2

Wavenumber,cm-1

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Experimental IR spectra of generations G’2v and the difference IR spectra (G’3v – G’2v) and (G’2 – G’2v)

1800 1600 1400 1200 1000 800 600 400

G'2v

G'2v

G'2

G'3v

G'2v

Wavenumber,cm-1

CONCLUSIONS

1. Based on analysis of vibrational spectra series of 12 generations phosphorus dendrimers the main features of their structure were derived. It was shown that practically the same spectral picture of dendrimers started from the 2-3 generation and higher is derived by relation of terminal groups and repeated units. The zero and first generation have different structure phase state.

2. Theoretical bases for the calculation of vibrational spectra of complex molecules of dendrimers in the frame of the fragment approximation are presented.

3. The analysis of the difference vibrational spectra of dendrimers leaned on the peculiarities of its structure. The obtained results expand the possibilities of vibrational spectroscopy in analysis of conformational state, electronic effects and so on.

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Publications. 

1. Kovalenko V.I., Furer V.L., Vandyukov A.E., Shagidullin R.R., Majoral J.P., Caminade A.-M. The Vibrational spectra of the elementoorganic starburst dendrimers.

J. Mol. Struct., 2002, v.604, 45-56.2. Furer V.L., Kovalenko V.I., Vandyukov A.E., Majoral J.P., Caminade A.M.,

Calculation of IR spectra of the elementorganic dendrimers. Spectrochim. Acta А, 2002, v.58, 2905-2912. 3. Furer V.L., Kovalenko V.I., Vandyukov A.E., Majoral J.-P., Caminade A.M..The vibrational analysis of the starting "monomer" and first generation of the starburst elementorganic dendrimer. Vibr. Spectr., 2003, v.31, No1, 71-79.4. Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I.

Fourier-Transform Infrared and Raman Difference Spectroscopy Studies of the Phosphorus-

containing dendrimers. Spectrochim. Acta А, 2004, v.60, 1649-1657.5. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT

calculation of molecular structure and vibrational spectra of the phosphorus-containing G’1 generation dendrimer with terminal aldehyde groups. Chem. Phys., 2006, v.326, 417-424

6. Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I. DFT study and IR spectra of the phosphorus-containing G1 generation dendrimer.

J. Mol. Struct. 2006, v.785, 133-138.7. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT study and

vibrational spectra of the phosphorus-containing G’0 generation dendrimer Vibr. Spectrosc., 2006, 40, No2, pp. 155-160

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10. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT calculation of molecular structure and vibrational spectra of the phosphorus-containing G’1 generation dendrimer with terminal aldehyde groups. Chem. Phys., 2006, v.326, 417-424

11. Furer V.L., Vandyukov A.E., Majoral J.P., Caminade A.M., Kovalenko V.I. DFT study and IR spectra of the phosphorus-containing G1 generation dendrimer.

J. Mol. Struct. 2006, v.785, 133-138.12. Furer V.L., Vandyukov A.E., Majoral J.-P., Caminade A.-M., Kovalenko V.I. DFT study

and vibrational spectra of the phosphorus-containing G’0 generation dendrimer Vibr. Spectrosc., 2006, 40, No2, pp. 155-160

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Thanksgiving:Сaminade A.-M., Majoral J.-P.

Laboratorie de Chimie de Coordination, CNRS, Toulouse, France

Kovalenko V.I., Vandyukov A.E., Vandyukova I.I. A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Science, Kazan, Russia

RFFI №99-03-33477а,АST 07-7.4-133/2002(Ф)

DCMS RAS program №7 2003-2007for financial support

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