supplementary material - nature · web viewsynthesis and single crystal solution of the organic...

SUPPLEMENTARY MATERIAL

1 Synthesis and single crystal solution of the Organic Structure Directing

Agent (OSDA)

2 Study of the self-assembling of the OSDA by Photoluminiscence

spectroscopy

3 Synthesis of ITQ-29 zeolites

4 Structure refinement of SiGe-LTA and pure silica LTA

5 Comparison of commercial LTA samples with ITQ-29 zeolites

1

1 Synthesis and single crystal solution of the Organic Structure-

Directing Agent

a Synthesis of the structure directing agent

The preparation of the starting amine followed a general synthetic

procedure previously described in the literature [H Katayama E Abe K

Kaneko J Heterocyclic Chem (1982) 19 925-926]

47 g of aniline (005 mol) 212 g of sodium carbonate (02 mol) and

1264 g of 1-bromo-3-chloropropane (075 mol) were added to a reaction vessel

equipped with magnetic stirring and a condenser The reaction mixture was

heated with vigorous stirring under nitrogen atmosphere by increasing gradually

the temperature (from 70ordmC during 1h to 160ordmC for 24h) After cooling the

solution was basified with NaOH and extracted with 3 portions of ether The

organic extracts were collected washed with water and treated with 2N

hydrochloric acid The resulting acidic extract was basified with NaOH and

extracted with ether The ether extract was washed with brine and dried over

anhydrous Na2SO4 The solvent was evaporated under reduced pressure to

give the amine in 85 yield The amine was quaternized with methyl iodide as

follows A 250 ml round bottom flask was charged with 10 g (00578 mol) of

amine and 100 ml of CHCl3 A solution of 245 g (0173 mol) of methyl iodide

was added and the reaction mixture was stirred at room temperature for three

days then new excess of methyl iodide (0173 mol) was added and stirred at

room temperature for 3 days After 3 days new excess of methyl iodide (0173

mol) was added and stirred at room temperature for three days After this time a

2

solid was collected by filtration washed exhaustively with ether and dried The

resulting ammonium salt was obtained in 897 yield

Characterization data 13C-NMR (200 MHz CD3OD) 1755 2517 5242

65051305413122131821407 ppm

Anal Calcd for C13H18NI() C495 H57 N44

Found C496 H58 N45

b Single crystal solution of the structure directing agent (OSDA)

The structure of the 4-methyl-2367-tetrahydro-1H5H-pirido[321-ij]-

quinolinium was determined by single crystal diffraction

Crystallographic data Formula [C13H18N]+I H2O Triclinic space group P1 a =

107663(2) Aring b = 135874(3) Aring c = 180131(4) Aring = 79993(2)ordm =

89723(2)ordm = 89564(2)ordm V = 259489(9) Aring3 Z = 8 (CuK) = 154178 Aring

A colourless single crystal of approximate dimensions 028 026

018 mm with prismatic shape was mounted on a glass fibber and transferred to

a Bruker SMART 6K CCD area-detector three-circle diffractometer with a MAC

Science Co Ltd Rotating Anode (Cu K radiation = 154178 Aring) generator

equipped with Goebel mirrors at settings of 50 kV and 100 mA X-Ray data

were collected at 100K with a combination of seven runs at different and 2

angles 4200 frames The data were collected using 03ordm wide scans (5

3

secframe at 2 = 40ordm and 15 secframe at 2 = 100ordm ) crystal-to-detector

distance of 40 cm

The substantial redundancy in data allows empirical absorption

corrections (SADABS) to be applied using multiple measurements of symmetry-

equivalent reflections (Ratio of minimum to maximum apparent transmission

0572573) A total number of 18657 reflections were collected with 8322

independent reflections (Rint = 00456 and Rsigma = 00561) The unit cell

parameters were obtained by full-matrix least-squares refinements of 8832

reflections

Crystallographic details are given in the attached OSDAcif file

The raw intensity data frames were integrated with the SAINT program

which also applied corrections for Lorentz and polarization effects

The software package SHELXTL version 610 was used for space group

determination structure solution and refinement The structure was solved by

direct methods (SHELXS-97) completed with difference Fourier syntheses and

refined with full-matrix least-squares using SHELXL-97 minimizing (F02 ndash Fc

2)2

Weighted R factors (Rw) and all goodness of fit S are based on F2 conventional

R factors (R) are based on F All non-hydrogen atoms were refined with

anisotropic displacement parameters All scattering factors and anomalous

dispersions factors are contained in the SHELXTL 610 program library The

hydrogen atom positions were calculated geometrically and were allowed to ride

on their parent carbon atoms with fixed isotropic U

The most streaking feature of the structure directing agent is that the

organic cations appear as two self-assembled moieties by an interaction

4

between aromatic rings that trend to locate parallel one respect each other at a

distance of approximately 2 Aring as it is presented in figure 1A

Figure 1A Molecular simulation for the structure of minimum energy

References

Bruker AXS SHELXTL version 610 Structure Determination Package Bruker

AXS 2000 Madison WI

Sheldrick GM SHELXS-97 Program for Structure Solution Acta Crystallogr

Sect A 1990 46 467

Sheldrick GM SHELXL-97 Program for Crystal Structure Refinement

Universitaumlt Goumlttingen 1997

Sheldrick GM SADABS version 203 a Program for Empirical Absorption

Correction Universitaumlt Goumlttingen 1997-2001

SAINT+ NT ver 604 SAX Area-Detector Integration Program Bruker AXS

1997-2001 Madison WI

SMART v 5625 Area-Detector Software Package Bruker AXS 1997-2001

Madison WI

5


spectroscopy

A UV-Vis Spectra of the OSDA in water solution The inset shows the

appearance of a new band that is assigned to the dimer formation which

increases as the OSDA concentration does (see reference 16 of the

manuscript)

6

B Photoluminescence spectrum (ex=265 nm) of the diluted OSDA in water

solution (1middot10-4 M) purged with nitrogen showing a single emission band

at approx 300 nm which is assigned to the OSDA as monomer

7

Monomer

C Photoluminiscence spectrum (ex=265 nm) of the 03 M OSDA aqueous

solution as hydroxide (This is the same concentration than that used for

the synthesis of ITQ-29) It is observed the presence of an intense

emission band at ca 450 nm The red-shift with respect to the monomer

spectrum has been attributed to the presence of π-stacking interactions

between adjacent aromatic rings (ref 16)

8

D Solid state Photoluminiscence spectrum (ex=265 nm) of the Iodide salt

of the OSDA It is seen that this spectrum is very similar to that obtained

in concentrated solution Since single crystal diffraction has shown that

the OSDA crystallised as dimers (see part 1 of this supplementary

material) we can unambiguously assigned the observed red-shift of the

emission to the π-stacking interactions between neighbored aromatic

rings Also the same interpretation could be valid for the most

concentrated aqueous solution (spectrum shown above)

9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)

E Solid state Photoluminiscence spectrum (ex=265 nm) of a ITQ-29 zeolite

(sample SR346b) in the as-prepared form

It is observed the presence of two emission bands at ca 310 and 430 nm

which were assigned to the OSDA as monomer and dimer respectively The

highest intensity of the second band indicates that most of the OSDA is

located inside of the ITQ-29 pores forming self-assembled dimers This is

further supported by chemical analyses and 13C-CP-MAS-NMR

spectroscopy (see supplementary material 3)

10

3 Synthesis and characterization of ITQ-29 zeolites

I Detailed synthesis methods

a) Al-free ITQ-29 (sample SR346B) was synthesized in fluoride media in the

presence of Ge from a gel of the following molar composition

067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O

The gel was prepared by hydrolyzing tetraethylorthosilicate (TEOS) in an

aqueous solution of 4-methyl-2367-tetrahydro-1H5H-pyrido[321-ij]

quinolinium hydroxide (ROH) then the appropriate amount of GeO2 was added

and the mixture was kept under stirring until the ethanol formed upon hydrolysis

of TEOS and the appropriate excess of water were evaporated to reach the gel

composition given above Finally an aqueous solution of HF (50) was added

and the mixture was introduced in a Teflon-lined stainless autoclave and heated

at 150ordmC for 5 days

After this time the autoclave was cooled down and the mixture was

filtered washed with water and dried at 100ordmC The final composition is given in

Table 1 The zeolite was calcined at 700ordmC in air

b) Al-containing ITQ-29 (sample SR386B) was synthesized in fluoride media in

the presence of Ge from a gel of the following composition

067 SiO2 033 GeO2 002 Al2O3 05 ROH 05 HF 7 H2O

11

The gel preparation was similar to that described for the Al-free ITQ-29

with the addition of Al isopropoxide as the source of Al and seeds of ITQ-29

(5 of the total inorganic oxides) in order to promote the crystallization

The crystallization was also carried out at 150ordmC for 5 days The final

composition is given in Table 1

c) The high Al content ITQ-29 zeolite (sample SR408A) was synthesized using

a mixture of OSDAacutes the quinolinium derivative and tetramethylammonium It

was obtained from a gel of the following composition

067 SiO2 033 GeO2 007 Al2O3 025 ROH 025 TMAOH 05 HF 7 H2O

The gel was prepared in a similar way than the previously described but adding

the required amount of tetraethylamonium hydroxide (TAMOH) together with the

quinolinium derivative hydroxide and seeds (5 of the total inorganic oxides) in

order to promote the crystallization The synthesis was carried out at 150ordmC for

3 days The final composition is given in Table 1

d) Purely siliceous ITQ-29 (sample SR455C) was prepared in fluoride media

from a gel of the following composition

100 SiO2 025 ROH 025 TMAOH 05 HF 2 H2O

The gel was prepared as described for SR346B but the addition of GeO2

was skipped and the crystallization was done at 135ordmC for 7 days The final

composition is given in table 1 The zeolite obtained was calcined at 700ordmC in

air

12

e) The Al-ITQ-29 zeolite employed for the catalytic experiments (Sample

SR454A) was synthesized from a gel of the following composition


The crystallization was performed at 135ordmC for 2 days The final composition is

given in Table 1

The zeolite was previously calcined at 580ordmC for 3 hours in air flow

before the catalytic experiments

f) Pure silicoaluminate ITQ-29 zeolite (sample SR452B) was synthesized using



100 SiO2 001 Al2O3 025 ROH 025 TMAOH 05 HF 3 H2O


the required amount of tetraethylamonium hydroxide (TMAOH) together with the

quinolinium derivative hydroxide and seeds of pure silica LTA (10 of the total

inorganic oxides) in order to promote the crystallization The synthesis was

carried out at 135ordmC for 5 days The final composition is given in Table 1

The XRD pattern shows that Al-ITQ-29 was obtained with a small impurity of

RUB-10 The Al-MAS-NMR spectrum shows a single resonance at approx 55

ppm indicating the tetrahedral coordination of Al in the sample Also this

sample when calcined was able to interact with ammonia and acetonitrile

showing the accessibility of the acid sites for small molecules

13

II Chemical analyses and 13 C-CP-MAS-NMR spectroscopy characterization

results

The chemical compositions of the ITQ-29 samples described above are given in

Table 1

Table 1 Chemical compositions of ITQ-29 samples expressed as molar composition per unit cellSample Si

(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15

(a) Calculated from the N content

(b) Calculated from the N and C contents and assuming no decomposition of

the OSDA

14

Figure 3a 13C-CP-MAS-NMR spectra of the as-prepared ITQ-29 zeolites indicates the spinning side bands

The 13C-NMR spectra indicate that the OSDA remains nearly intact within

the pores of the ITQ-29 zeolites as deduced from the close resemblance of the

solid NMR spectra and the liquid phase spectrum of an aqueous solution of the

OSDA In the spectra of the samples prepared in presence of TMAOH a new

signal at 58 ppm (marked as ) appears indicating that TMA+ cations are

incorporated into the solids Finally some minor decomposition products are

also detected (marked as )

15

4 Structure Refinement of SiGe-LTA and pure silica LTA

Structure refinement of Ge containing ITQ-29 sample (SiGe = 2)

The calcined sample with SiGe molar ratio of 21 was measured in

vacuum and the corresponding X ray powder diffraction (XRD) pattern is shown

in Figure 4a This pattern was also indexed according to a cubic unit cell with

refined cell parameter equal to 120157(4) Aring For the Rietveld refinement the

LTA zeolite structure type with Pm3m space group symmetry was employed

According to the refined scattering power at the T site and assuming that it is

filled the unit cell composition of the calcined sample is Si166 Ge74 O48 ie the

refined SiGe ratio is 22 The averaged distance (d) and angles ( ) from the

tetrahedron are d(T-O)=162Aring (O-T-O) =1094ordm (T-O-T) = 1531ordm The

refined atomic coordinates are listed in Table 2 and Figure 4a shows the very

good agreement between observed and calculated XRD patterns The details of

the Rietveld refinement are given in the Experimental Section

Table 2 Fractional atomic coordinates[ab] for ITQ-29 (SiGe=22)

Atom x y z No of positions

Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m

[a] As obtained from Rietveld refinement (space group Pm3m a=120157(4)Aring)[b] Estimated standard deviations given in parentheses[c] Refined atomic occupations for site T 069(2)Si+031(2)Ge

16

Figure 4a Observed (crosses) and calculated (lines) XRD patterns of ITQ-29 as well as the difference profile (bottom) The short tick marks below the pattern give the positions of Bragg reflections The arrows indicate the tow small regions excluded from the Rietveld refinement containing the diffraction lines of the platinum sample holder (Cu K12 radiation)

Structure refinement of pure silica ITQ-29 sample

The purely siliceous sample was measured after calcination at 700ordmC

under air and the corresponding X ray powder diffraction (XRD) pattern is

shown in Figure 4b This pattern was indexed according to a cubic unit cell with



The refined atomic coordinates are given in Table 3 and Figure 4b shows the

very good agreement between observed and calculated XRD patterns which

confirms that ITQ-29 has LTA structure type

17

Table 3 Fractional atomic coordinates[ab] for pure silica ITQ-29


Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m

[a] As obtained from Rietveld refinement (space group Pm3m a=118671(4)Aring)[b] Estimated standard deviations given in parentheses

Figure 4b Observed (crosses) and calculated (lines) XRD patterns of pure silica zeolite A as well as the difference profile (bottom) The short tick marks below the pattern give the positions of Bragg reflections (Cu K12 radiation) To emphasize the high angle portion of the pattern the first reflection has been cut at half height

The refined unit cell volume is shorter by 64 Aring3 than the volume found for

the Ge containing form (ie 1671 Aring3 in front of 1735 Aring3) This result is consistent

with the larger ionic radius of Ge compared to Si that is also responsible of the

larger averaged T-O distance obtained in the Ge zeolite (d(T-O)=162Aring) than in

18

the pure silica ITQ-29 material (d(Si-O)=160Aring) The averaged distance (d) and

angles ( ) from the tetrahedron are d(Si-O)=160Aring (O-Si-O) = 1094ordm (Si-

O-Si) = 1533ordm It is notorious (see Table 4) that the most tensioned Si-O-Si

angle is the Si-O2-Si angle (1584ordm) which correspond to the oxygen that is

linking to neighboured D4R cages On the other hand the Si-O-Si angles

corresponding to oxygen atoms placed at that small D4R cage do not seem to

be strongly constrained giving Si-O1-Si and Si-O3-Si angles of 1517 and

1497ordm respectively

Table 4 Bond distances in Aring and bond angles in (ordm) with esds in parentheses

for pure Si zeolite A

Si - O1 1612(5)Si - O2 1568(7)Si - O3 1606(7) (2x)O1 - Si - O2 1102(4)O1 - Si - O3 1085(5) (2x)O2 - Si - O3 1106(6) (2x)O3 - Si - O3 1085(7)Si - O1 -Si 1517(6)Si- O2 - Si 1584(9)Si - O3 - Si 1497(9)

The details of the Rietveld refinement are given in the Experimental Section

Experimental section

XRD

The Ge containing ITQ-29 sample was calcined at 700ordmC for 1 hour The

pattern was measured at room temperature in vacuum on a Philips XPert

diffractometer with Bragg-Brentano geometry using a Pt sample holder and an

19

XCelerator detector Intensity data obtained with fixed divergence slit (025ordm)

Cu K radiation ( = 15406 15444Aring) Tube voltage and intensity 45 kV and

40 mA Step size and time 0017ordm 2 and 6000s

The pure silica ITQ-29 sample was calcined at 700ordmC in air for 3 hours

The pattern was measured at room temperature on a Philips XPert

diffractometer with Bragg-Brentano geometry using a conventional flat stage

holder and an XCelerator detector Intensity data obtained with fixed

divergence slit (0125ordm) Cu K radiation ( = 15406 15444Aring) Tube voltage

and intensity 45 kV and 40 mA Step size and time 0017ordm 2 and 6000s

Rietveld refinement

The Rietveld refinement of Ge-ITQ-29 data was performed with LSP7

using a 2 range from 135ordm to 642ordm with the regions between 39344 - 40177

and 45701 - 47220 excluded due to the appearance in these regions of the

(111) and (200) Pt diffraction peaks of the sample holder The transmission

coefficient at the Pt(111) Bragg position is 035 which was used for correcting

the finite film thickness of the sample Number of contributing reflections is 86

No geometric restraints used Number of structural parameters is 7 Number of

profile parameters is 8 including unit cell parameters and zero shift (-0020ordm 2)

with visually estimated background (Average background = 38000 counts)

Profile function used was Pearson VII Refined overall thermal vibration

coefficient B = 60Aring2 The residuals of the refinement were Rwp=0026

Rp=0018 2=50

The Rietveld refinement of the pure silica-ITQ-29 data with LSP7 was

performed using the measured 2 range from 5ordm to 75ordm Number of contributing

20

reflections is 186 No geometric restraints used Number of structural

parameters is 7 Number of profile parameters is 8 including unit cell

parameters and zero shift (-0055ordm 2) with visually estimated background

(Average background = 400 counts) Profile function used was Pearson VII

Refined overall thermal vibration coefficient B = 07Aring2 The residuals of the

refinement were Rwp=0097 Rp=0062 RB=0032 2=28

21


The XRD patterns of different commercial LTA zeolites are given for

comparison purposes

Zeolite 3A is the potassium form of the LTA zeolite having the following

composition

06 K2O 040 Na2O 1 Al2O3 20 plusmn 01SiO2 x H2O

4A is the same zeolite but in the sodium its formula is

1 Na2O 1 Al2O3 20 plusmn 01 SiO2 x H2O

Finally 5A is the Ca2+ exchanged material with the following composition

080 CaO 020 Na2O 1 Al2O3 20 plusmn 01 SiO2 x H2O

(all of them were purchased from Aldrich Co)

As can be seen all the commercial LTA samples posses a framework SiAl ratio

close to 1

22

In the figure It can be seen there that the peak intensities greatly depend on the

nature of the exchanged cation located within the cavities of the LTA structure

Also the X-ray diffraction lines of pure silica ITQ-29 zeolite are shifted towards

low 2θ values (ie higher d spacing) due to the smaller ionic radii of Si than that

of Al However the formation of pure silica LTA can be unambiguously

confirmed from the absence of non assigned diffraction lines and the goodness

of Rietveld refinement

23


1 Synthesis and single crystal solution of the Organic Structure-

Directing Agent

a Synthesis of the structure directing agent

The preparation of the starting amine followed a general synthetic

procedure previously described in the literature [H Katayama E Abe K

Kaneko J Heterocyclic Chem (1982) 19 925-926]

47 g of aniline (005 mol) 212 g of sodium carbonate (02 mol) and

1264 g of 1-bromo-3-chloropropane (075 mol) were added to a reaction vessel

equipped with magnetic stirring and a condenser The reaction mixture was

heated with vigorous stirring under nitrogen atmosphere by increasing gradually

the temperature (from 70ordmC during 1h to 160ordmC for 24h) After cooling the

solution was basified with NaOH and extracted with 3 portions of ether The

organic extracts were collected washed with water and treated with 2N

hydrochloric acid The resulting acidic extract was basified with NaOH and

extracted with ether The ether extract was washed with brine and dried over

anhydrous Na2SO4 The solvent was evaporated under reduced pressure to

give the amine in 85 yield The amine was quaternized with methyl iodide as

follows A 250 ml round bottom flask was charged with 10 g (00578 mol) of

amine and 100 ml of CHCl3 A solution of 245 g (0173 mol) of methyl iodide

was added and the reaction mixture was stirred at room temperature for three

days then new excess of methyl iodide (0173 mol) was added and stirred at

room temperature for 3 days After 3 days new excess of methyl iodide (0173

mol) was added and stirred at room temperature for three days After this time a

2




65051305413122131821407 ppm


Found C496 H58 N45














3


distance of 40 cm







reflections








2)2









4




References


AXS 2000 Madison WI


Sect A 1990 46 467








Madison WI

5


spectroscopy




manuscript)

6




7

Monomer







8









9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23





65051305413122131821407 ppm


Found C496 H58 N45














3


distance of 40 cm







reflections








2)2









4




References


AXS 2000 Madison WI


Sect A 1990 46 467








Madison WI

5


spectroscopy




manuscript)

6




7

Monomer







8









9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23



distance of 40 cm







reflections








2)2









4




References


AXS 2000 Madison WI


Sect A 1990 46 467








Madison WI

5


spectroscopy




manuscript)

6




7

Monomer







8









9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23





References


AXS 2000 Madison WI


Sect A 1990 46 467








Madison WI

5


spectroscopy




manuscript)

6




7

Monomer







8









9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23



spectroscopy




manuscript)

6




7

Monomer







8









9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23





7

Monomer







8









9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23








8









9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23










9

300 400 500

80000

120000

160000

200000

Cou

nts

(au

)

Wavelength (nm)









10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23










10





067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23






067 SiO2 033 GeO2 05 ROH 05 HF 7 H2O















11





















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23






















air

12





given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23






given in Table 1

















13


results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23



results


Table 1


(uc)Ge (uc)

Al (uc)

C (uc)

N(uc)

F(uc)

OSDA(uc)

TMA(uc)

SR346B 164 76 --- 278 21 20 21(a) 0

SR386B 155 82 03 284 23 16 23(a) 0

SR408A 145 78 17 305 31 10 20(b) 10

SR455C 240 --- --- 282 30 20 18(b) 12

SR454A 207 21 12 312 30 12 21(b) 09

SR452B 235 --- 05 294 33 18 18(b) 15



the OSDA

14









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23









15

















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23


















Wyckoff notation

T[c] 03700(1) 01840(1) 0 24 k

O1 12 02118(5) 0 12 h

O2 02946(5) 02946(5) 0 12 i

O3 03370(3) 01095(4) 01095(4) 24 m


16











17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23












17



Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23




Wyckoff notation

Si 03683(3) 01847(3) 0 24 k

O1 12 02179(7) 0 12 h

O2 02939(7) x 0 12 i

O3 03429(4) 01098(7) y 24 m







18














XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23















XRD




19










Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23











Rietveld refinement












Rp=0018 2=50



20







21



comparison purposes


composition








close to 1

22








23








21



comparison purposes


composition








close to 1

22








23




comparison purposes


composition








close to 1

22








23









23


supplementary material - nature · web viewsynthesis and single crystal solution of the organic...

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