Electronic Supplementary Material (ESI) for New Journal of Chemistry.
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016
Hybride halobismuthate light-harvesting material with optical band gap of 1.70 eV
Vitalii Yu. Kotov, Andrey B. Ilyukhin, Kirill P. Birin, Veronika K. Laurinavichyute, Alexey A.
Sadovnikov, Zhanna V. Dobrokhotova, Sergey A. Kozyukhin
Electronic supplementary information
Synthesis of Bis(4-cyano-1-pyridino)propane bromide
Bis(4-cyano-1-pyridino)propane bromide was synthesized with 4-pyridinecarbonitrile
(Aldrich 98%) and 1,3-dibrompropane C3H6Br2 (Aldrich 97%). The reaction mixture of 5 ml 1,3
–dibrompropane, 10 ml acetonitrile and 20 g of 4-pyridinecarbonitrile was refluxed for 1 hour.
After the mixture had been cooled down to room temperature, 100 ml of 95% ethyl alcohol was
added and the mixture was boiled for another 3-5 minutes. The hot solution was filtered under
vacuum. The filtered precipitate A was washed with acetone, and then dried at room
temperature. The supernatant solution was stored for another 24 hours. The precipitate B formed
during this period was separated, washed with acetone and then dried in air.
Bis(4-cyano-1-pyridino)propane bromide (C15H14N4)Br2 (PyС3Br2) was isolated as a
light yellow precipitate A (74.2% yield, the content of main component– 97%, NMR) and a
beige precipitate B (3.4% yield, the content of main component – 100%, NHR). NMR
(300 MHz, D2O): 9.23 (d, 4H), 8.52 (d, 4H), 4.92 (t, 4H), 2.87 (p, 2H).
Synthesis of bis(4-cyano-1-pyridino)propane bromobismuthate
a
Fig.S1. (a) Initial milky white precipitate for the reaction PyC32+ + Br- + BiBr4-, (b) orange
precipitate formed when reaction mixture stirred at room temperature for 1-2 min.
b
Synthesis of bis(4-cyano-1-pyridino)propane bromoiodobismuthate
Fig.S2. From left to right: 1, 2a, 2b, 2c, 2d, 2.
1H NMR analysis of bis(4-cyano-1-pyridino)propane halobismuthates
Fig.S3. 1H NMR spectrum of 1 in DMSO d6.
Fig.S4. 1H NMR spectrum of 2 in DMSO d6.
Fig.S5. 1H NMR spectrum of 3 in DMSO d6.
Structure description
Table S1. Selected bond lengths [Å] and angles [°] for 1
Bi(1)-Br(1)
Bi(1)-Br(4)
Bi(1)-Br(5)
Bi(1)-Br(3)
Bi(1)-Br(2)
Bi(1)-Br(1)#1
Br(1)-Bi(1)-Br(4)
Br(1)-Bi(1)-Br(5)
Br(4)-Bi(1)-Br(5)
Br(1)-Bi(1)-Br(3)
Br(4)-Bi(1)-Br(3)
Br(5)-Bi(1)-Br(3)
Br(1)-Bi(1)-Br(2)
Br(4)-Bi(1)-Br(2)
Br(5)-Bi(1)-Br(2)
Br(3)-Bi(1)-Br(2)
Br(1)-Bi(1)-Br(1)#1
Br(4)-Bi(1)-Br(1)#1
Br(5)-Bi(1)-Br(1)#1
Br(3)-Bi(1)-Br(1)#1
Br(2)-Bi(1)-Br(1)#1
Bi(1)-Br(1)-Bi(1)#2
2.7442(7)
2.7841(7)
2.8170(7)
2.8654(7)
2.8672(7)
3.0780(7)
89.71(2)
92.85(2)
89.23(2)
86.41(2)
175.86(2)
92.44(2)
88.89(2)
88.49(2)
177.13(2)
89.95(2)
175.059(15)
85.90(2)
84.81(2)
98.02(2)
93.28(2)
159.10(3)
Symmetry transformations used to generate equivalent atoms:
#1 x+1/2,y,-z+3/2 #2 x-1/2,y,-z+3/2
Thermal stability of bis(4-cyano-1-pyridino)propane halobismuthates
Fig.S6. TGA and DTA curves of 1.
Fig.S7. TGA and DTA curves of 2.
Fig.S8. TGA and DTA curves of 3.
X-ray analysis of powders
5
4
3
2
1
2, o
10
20
30
Fig.S9. XRD curves of 2a (1), 2b (2) 2c (3), 2d (4), 2 (5).
40
50
1
2
3
10
20
30
2,
40
o
Fig.S10. XRD curves of 2 (1), 2 after heating 1h at 100oC (2), 2 after heating 6h at 160oC (3).
1
2
10
20
30
2,
Fig.S11. XRD curves of 3 (1), 3A (2),
o
40
50
Absorption spectrum
0.8
A
Model
Gauss
Equation
y=y0 + (A/(w*sqrt(PI/2)))*exp(-2*((x-xc)/w)^2
)
Reduced ChiSqr
1.54433E-5
Adj. R-Square
0.99967
Value
0.6
0.4
0.2
0.0
12000
Standard Erro
Peak1(B)
y0
0.04573
0.00532
Peak1(B)
xc
16222.8836
89.45295
Peak1(B)
w
3121.3831
97.02294
Peak1(B)
A
1572.69142
148.66466
Peak1(B)
sigma
1560.69155
Peak1(B)
FWHM
3675.14774
Peak1(B)
Height
Peak2(B)
y0
0.04573
0.00532
Peak2(B)
xc
20194.8975
126.48724
Peak2(B)
w
3612.1219
337.37402
Peak2(B)
A
3135.92254
409.83209
Peak2(B)
sigma
1806.06095
Peak2(B)
FWHM
4252.94852
Peak2(B)
Height
Peak3(B)
y0
0.04573
0.00532
Peak3(B)
xc
22719.7768
127.37434
Peak3(B)
w
2195.39157
313.66357
Peak3(B)
A
1168.39029
460.8349
Peak3(B)
sigma
1097.69578
Peak3(B)
FWHM
2584.87603
Peak3(B)
Height
0.42464
0.40201
0.6927
,cm-1
14000
16000
18000
20000
22000
24000
26000
Fig.S12. Absorption spectrum of 2c and its devolution into the Gaussian components.
EDX analysis data
Fig.S13. EDX analysis data for 1.
Fig.S14. EDX analysis data for 2.
Fig.S15. EDX analysis data for 2a.
Fig.S16. EDX analysis data for 2b.
Fig.S17. EDX analysis data for 2c.
Fig.S18. EDX analysis data for 2d.
Fig.S19. EDX analysis data for 3.
1.0
N`
0.8
0.6
0.4
0.2
N
0.0
0.0
0.2
0.4
0.6
0.8
1.0
Fig. S20. Fraction of I (N` = I/(I+Br), mol% , EDX) in solid 1, 2a,2b, 2c, 2d, 2 and 3 vs fraction
I in initial mixture (N).