Supporting Imformation
Effects of Hydrogen Bond and Solvent Polarity on the C=O Streching and
Photophysical Properties of bis(2-thienyl)ketone in Solution
Huigang Wang*a,b,c, liBo Wang a,b, Shaosong Shen a,b, Wenfei Zhang a,b, Mingde Li c, Lili Du c, Xuming Zheng* a,b,David Lee Phillipsc
a
Department of Chemistry and State Key Laboratory of advanced Textiles Materials and Manufacture Technology, MOE, Zhejiang Sci-Tech University, Hangzhou
310018, China
b
Engineering Research Center for Eco-dyeing and Finishing of Textiles, MOE, Zhejiang Sci-Tech University, Hangzhou 310018, China
c
Department of Chemistry, The University of Hong Kong, Pokfulam Road,Hong Kong S.A.R., P. R. of China
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[E]
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[D]
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*
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*
[C]
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[B]
[A]
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2800 3000 3200 3400
-1
Ramanshift(cm )
Figure S1 Simulated Raman spectra within the frame work of (A)DFT levels of theory with B3LYP/6-311G* basis set. Experimental Raman spectra with excitation
wavelength 252.7 nm(B) in crystal state, (C)in cyclohexane, (D)in methanol, (E) in acetonitrile solutions. Asterisks indicate respective solvent bands.
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[E]
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[D] * *
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[C]
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[B]
[A]
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2800 3000 3200 3400
-1
Ramanshift(cm )
Figure S2 Simulated Raman spectra within the frame work of (A)DFT levels of theory with B3LYP/6-311G* basis set. Experimental Raman spectra with excitation
wavelength 266 nm(B) in crystal state, (C)in cyclohexane, (D)in methanol, (E) in acetonitrile solutions. Asterisks indicate respective solvent bands.
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[E]
[D]
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[C]
[B]
[A]
200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400
-1
Ramanshift(cm )
Figure S3 Simulated Raman spectra within the frame work of (A)DFT levels of theory with B3LYP/6-311G* basis set. Experimental Raman spectra with excitation
wavelength 282.4 nm(B) in crystal state, (C)in cyclohexane, (D)in methanol, (E) in acetonitrile solutions. Asterisks indicate respective solvent bands.
[E]
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[D]
[C]
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[B]
[A]
200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400
-1
Ramanshift(cm )
Figure S4 Simulated Raman spectra within the frame work of (A)DFT levels of theory with B3LYP/6-311G* basis set. Experimental Raman spectra with excitation
wavelength 319.9 nm(B) in crystal state, (C)in cyclohexane, (D)in methanol, (E) in acetonitrile solutions. Asterisks indicate respective solvent bands.

12 14
9 10
7
10+7
 9 + 7
27
210
10+33
10+29
7+33
7+29
10+19
10+17
20
19

2933
25
FT-Raman
319.9 in C6H12
Intensity
309.1 in C6H12
282.4 in C6H12
266 in C6H12
FT-IR
0
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-1
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4000
Ramanshift(cm )
Figure S5 Comparison of the FT-Raman, FT-IR, 319.9, 309.1, 282.4, 266.0 nm resonance Raman spectra of bis(2-thienyl)ketone
Relative Absorbance
[B]
[A]
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-1
Wavenumber(cm )
Figure S6.
[A]DFT levels of theory with B3LYP/6-311G* [B]IR spectrum of bis(2-thienyl)ketone (experiment)
1 0.00 s (LP Spectral Scan)
1 0.00 s
2 200.00 ns
3 400.00 ns
5 800 ns
6 1000 ns
7 1200 ns
0.10
0.08
0.06
0.04
0.02
0.00
350 400 450 500 550 600 650 700 750
Wavelength/nm
Figure S7.
nanosecond transient absorption spectra of bis(2-thienyl)ketone measured at 0, 200, 400, 800, 1000 and 1200 ns from top to bottom.
bis(2-thienyl)ketone-c6h12-662nm (LP Time Scan)
bis(2-thienyl)ketone-c6h12-662nm
ExpDec1 of bis(2-thienyl)ketone-c6h12-662
Equation
0.006
y = A1*exp(-x/t1) +
y0
Reduced Chi-Sqr
5.71076E-8
Adj. R-Square
0.91742
Value
0.003
Standard Error
ketone-c6h12-640 y0
-2.60569E-5
1.08529E-5
ketone-c6h12-640 A1
1.81957E30
3.59083E30
ketone-c6h12-640 t1
9.53065
0.25102
0.000
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1000
1200
Wavelength/nm
Figure S8. nanosecond transient absorption decays of bis(2-thienyl)ketone excited at 266 nm measured at 662 nm (lines) and the transient
absorption decay at 662 nm was fitted with a exponential functions: y = A1*exp(-x/τ) + y0. The table inserted shows the fitting parameters.
Integrated intensity (a.u.)
200 250 300 350 400 450 500 550 600 650 700
Wavelength/ nm
Figure S9 B3LYP-TD/6-311G(d) computed triplet excitons electronic absorption spectrum of bis(2-thienyl)ketone