New cyano functionalized silanes: Synthesis, characterization and diphenylamine detection

Article abstract of DOI:10.1016/j.jorganchem.2014.05.039

A series of novel tetrahedral silicon-centered cyano functionalized silanes, bis(4-cyanodiphenyl)dimethylsilane (1), bis(4-cyanodiphenyl) diphenylsilane (2), tri(4-cyandiphenyl)methylsilane (3), tri(4-cyandiphenyl) phenylsilane (4), and tetra(4-cyandiphenyl) silane (5), have been synthesized by Suzuki coupling reactions. They all display high thermal stability, and are fluorescent with strong emission in the region of violet to blue. Furthermore, 1-5 all exhibited the linear fluorescent quenching response to diphenylamine (DPA) with the high binding constants up to 1.0 × 10⁶ M ^-1 in dichloromethane solution, demonstrating the potential application in DPA detection.

Full text of DOI:10.1016/j.jorganchem.2014.05.039

Accepted Manuscript
New cyano functionalized silanes： Synthesis, characterization and diphenylamine
detection
Linlin Wang , Dengxu Wang , Hua Wang , Shengyu Feng
PII:
S0022-328X(14)00285-X
10.1016/j.jorganchem.2014.05.039
JOM 18611
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 25 June 2013
Revised Date: 26 May 2014
Accepted Date: 29 May 2014
Please cite this article as: L. Wang, D. Wang, H. Wang, S. Feng, New cyano functionalized silanes：
Synthesis, characterization and diphenylamine detection, Journal of Organometallic Chemistry (2014),
doi: 10.1016/j.jorganchem.2014.05.039.
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New cyano functionalized silanesꢀ Synthesis, characterization and
diphenylamine detection
Linlin Wang, Dengxu Wang, Hua Wang and Shengyu Feng*
Key Laboratory of Special Functional Aggregated Materials, Ministry of Education; School of
Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, PR China
* Corresponding author: Shengyu Feng
Tel.: (+86)531 8836 4866
Fax: (+86)531 8856 4464
E-mail: fsy@sdu.edu.cn
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ABSTRACTꢀA series of novel tetrahedral silicon-centered cyano functionalized silanes, bis(4-
cyanodiphenyl)dimethylsilane
(1),
bis(4-cyanodiphenyl)diphenylsilane
(2),
tri(4-
cyandiphenyl)methylsilane (3), tri(4-cyandiphenyl)phenylsilane (4), and tetra(4-cyandiphenyl)
silane (5), have been synthesized by Suzuki coupling reactions. They all display high thermal
stability, and are fluorescent with strong emission in the region of violet to blue. Furthermore, 1-
5 all exhibited the linear fluorescent quenching response to diphenylamine (DPA) with the high
binding constants up to 1.0×106 M-1 in dichloromethane solution, demonstrating the potential
application in DPA detection.
Keywords: Tetrahedral silicon; 4-cyanodiphenyl; fluorescent quenching; OLEDs; DPA
detection
1. Introduction
Luminescent materials based on tetrahedral silicon-centered organic small molecules have
recently attracted increasing attentions due to their potential applications in sensor technologies
as well as organic light emitting devices (OLEDs) [1-4]. Compared with the traditional organic
compounds, silicon-based molecules have many advantages such as well-defined structures, high
color purity and narrow emissions with high photoluminescence quantum yields [5-8].
Furthermore, they have been proved to have good film-forming properties with high glass-
transition temperature and high thermal stability, promoting the application in non-aggregating
amorphous electroluminescent devices [9-11]. Thus, a large number of silicon-cored molecules
have been designed, synthesized and applied in the area of highly efficient electroluminescent
devices [12-14].
Because of its structural simplicity and high polarizability, the cyano group has been
frequently utilized as a functional unit in the design of advanced electroluminescent materials
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[15-17]. The introduction of cyano group into electron transporting materials could produce high
electron mobility and a low electron injection barrier to improve the photoelectric properties [18-
19]. Meanwhile, the HOMO energy level can be drawn further downwards with the cyano group
introduction, which could meet the demand of exciton-blocking materials [20]. In addition, the
incorporation of the simple and small cyano group could significantly improve the
thermal/morphological stabilities of electroluminescent materials [21]. Thus the cyano group has
been widely used in the electroluminescent material design.
With the aim to develop more silanes for highly efficient organic luminescent materials, we
combined cyano group and silicon core into one system and synthesize a series of novel cyano
functionalized
silanes,
namely,
bis(4-cyanodiphenyl)dimethylsilane
tri(4-cyandiphenyl)methylsilane
(1)
bis(4-
tri(4-
cyanodiphenyl)diphenylsilane
(2),
(3),
cyandiphenyl)phenylsilane (4), and tetra(4-cyandiphenyl) silane (5). Luminescent property
investigations revealed that all of them exhibited strong violet-to-blue emission and displayed the
obvious linear fluorescent quenching response to DPA, which could be potentially used as the
fluorescence detector for DPA. Cyclic voltammetry (CV) and Molecular orbital calculations
were also carried out to investigate the possible application in OLEDs.
2 Results and discussion
2.1 Synthesis
Silicon-centered cyano functionalized silanes, 1-5, were synthesized according to the
synthetic routes described in Scheme 1. According to the previous reports [22-24],
bromophenyl-containing silanes, 6-10, were synthesized by reacting 1, 4-dibormobenzene with
the appropriate chlorosubstituted silanes. Then, Suzuki coupling reactions between 4-
cyanophenylboronic acid and bromophenyl-containing silanes provided these silicon-centered
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cyano functionalized silanes with high yields. Compound 1 was first synthesized in
tetrahydrofuran at 60ºC for 24 h with the low yield. To increase the reaction temperature, a
mixture of ethanol and toluene was used as the solvent and the yield of 1 increased up to 95%.
1
Thus, compounds 1-5 were effectively synthesized and characterized by FTIR, H NMR, 13C
NMR, 29Si NMR, HRMS and elemental analysis.
2.2 Thermal properties
The thermal properties of 1-5 were determined by the thermogravimetric analysis (TGA)
with a heating rate of 10 ºC /min under nitrogen. The results showed that 2-5 were stable up to
350 ºC while 1 decomposes at about 240 ºC, which may be owing to the lower thermal stability
of two Si-CH3 groups in 1 compared to other compounds with more Si-Ph groups. The
differential scanning calorimetry (DSC) analysis of 1 and 2 during the second heating cycle
detected the glass-transition temperature (Tg) at 174 ºC and 205 ºC, respectively. And the melting
points (Tm) of 1 and 2 were found at 215 ºC and 254 ºC, respectively. Only the melting points
(Tm) of 3-5 were observed at 187 ºC, 246 ºC and 264 ºC, respectively. All these results suggested
that compounds 1-5 possess high morphological stability, indicating the potentially practical
application in highly efficient luminescent materials.
2.3. Optical and electronic properties
To investigate the application possibilities of 1-5 in OLEDs, their UV-vis and luminescent
spectra were measured. As shown in Figure 1A, these compounds with the same functional
group all exhibit one similar intense absorption band with different molar absorption
coefficients. The absorption peaks at about 280 nm can be attributed to the π-π transitions
involving the phenyl and cyano groups. Meanwhile, 1-5 are all luminescent and emit a violet-
blue color in solution and in the solid state when irradiated by UV light. Similar to UV-vis
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absorption spectra, 1-5 all display the similar fluorescence spectra with the maximum emission
wavelength at about 333 nm in CH2Cl2 solution (Figure 1B). In the solid state, 1-5 possess high
quantum yield and display a narrow emission from violet to blue region with the emission
wavelength maximum ranging from 370 nm (3) to 388 nm (2) (Figure 1C and Table 1).
Moreover, the emission spectra in the solid state for 1-5 are considerably red-shifted compared
with that in solution, which may be caused by strong intermolecular interactions. In addition, 5
exhibit stronger emission and higher quantum yield than other four compounds, indicating that
different intermolecular interactions may exist in 5.
To gain insight into the electronic and optical properties of 1-5, CV experiment and
molecular orbital calculations were carried out [25-30]. The calculated and experimental data of
1-5 are summarized in Table 2. All the compounds exhibited irreversible oxidation waves. The
HOMO energy levels were estimated on the basis of the onset potential of the first oxidation
waves. The HOMO-LUMO energy gap values calculated from UV-vis absorption are all lower
than the energy gap values calculated by DFT, but still as high as 3.86 eV, which indicates the
possible application as blue emitters in OLEDs. In addition, these compounds with the same
functional group all possess the similar energy gaps, indicating the independent of functionality
for energy gap.
The orbital diagrams of the HOMOs and LUMOs of 1-5 are shown in Figure 2 (1, 2 and 3)
and Figure S19 (4 and 5). The HOMOs and LUMOs of these compounds are similar with
dominating contributions from the orbitals of the 4-cyanodiphenyl groups. The silicon atom has
no contribution to the HOMO or LUMO orbitals, indicating that the tetrahedral silicon has no
significant effect on electronic and optical properties of 1-5. Thus, silicon atom and phenyl ring
have limited dπ-pπ conjugation to induce the long conjugation of the whole molecule. These
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results may account for the blue-shifted UV-vis absorption and emission spectra of 1-5 compared
with previous reports on luminescent compounds used in OLEDs [31-33]. However, the
incorporation of silicon atom to these compounds can improve their color purity due to the
narrow emission, which makes them promising candidates for blue emitters in OLEDs displays.
2.4 Diphenylamine (DPA) detection
DPA is a diarylamine antioxidant. It has been widely used as a preservative or stabilizer in fruit
storage [34] and smokeless gunpowders [35-36]. DPA residues in fruits may cause health
problems, such as bladder symptoms, tachycardia, hypertension and skin problems, while the
DPA stabilizers residues in forensic science can provide valuable evidence in firearm discharge
cases [34-40]. Thus, the detection and identification of DPA in different environments has
become of great importance for security and forensic diagnostics. Many techniques have been
investigated for this purpose, such as gas chromatography coupled to mass spectrometry (GC-
MS) and liquid chromatography-mass spectrometry (LC-MS), cyclic voltammetry (CV) and
Raman spectroscopy [37-40]. But the majorities are not ideal for DPA detection in that they are
invasive or require sample preparation. Here, the fluorescence quenching method was tried to
detect DPA for the purpose of high sensitivity, easy visualization, and short response time for
detection.
As shown in Figure 3-4 and Figure S25-27, upon gradual addition of DPA to a
dichloromethane solution of 1-5, the initial fluorescence intensity was quenched efficiently. The
quenching response was studied by the Stern-Volmer equation and the corresponding calculated
Stern-Volmer binding constants were shown in Table 3. These results demonstrated that 1-5
possessed the high binding constants (Ksv) and correlation coefficient (R), indicating the good
linear response of fluorescence quenching in the low concentration of DPA. Thus, these
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compounds may be applied as the excellent candidates for the sensitive detection of DPA.
In addition, the UV absorption response to DPA of 1-5 and the calculated Stern–Volmer
equation were investigated (Figure 5 and S28-31). The UV absorption titration results revealed
that 1-5 all showed a linear UV absorption enhancement response with the addition of DPA.
However, compared with the fluorescence quenching for DPA, the Ksv and R values of UV
absorption response were relatively low (Table 4). Thus, the fluorescence quenching method
was more sensitive to detect DPA.
3 Conclusions
Aiming to develop the highly emissive organic luminescent materials, a series of novel cyano
functionalized silanes have been successfully synthesized and characterized. These compounds
all possess strong blue emission and display the obvious linear fluorescent quenching response to
diphenylamine (DPA) with high binding constants in dilute solution. Thus, these compounds
could be used for further development of efficient fluorescent sensors to detect DPA.
4 Experimental
4.1 General
Toluene was dried by distillation from the sodium ketyl of benzophenone. Unless otherwise
noted, all reagents were obtained from commercial suppliers and used without further
purification.
FTIR were recorded on a Bruker Tensor 27 spectrophotometer in the frequency range 4000-
1
13
29
400 cm-1 at a resolution of 4 cm-1 with a total of 16 scans. H NMR, C NMR and Si NMR
spectra were recorded on a Bruker AVANCE-400 NMR Spectrometer. High-resolution mass
spectra were obtained using positive mode on Agilent Technologies 6510Q-TOFLC-MS.
Elemental analyses (C, H, N) were measured on an Elementar Vario MICRO CUBE (Germany)
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elemental analyzer. TGA was performed with a Mettler Toledo SDTA-854 TGA system in
nitrogen atmosphere at a heating rate of 10 ºC /min. DSC curves were obtained by a Mettler
Toledo DSC882 in nitrogen at a heating rate of 10 ºC /min. The UV-vis spectra were determined
with TU-1901 double beam UV-vis spectrophotometer. The fluorescence spectra were
determined with HITACHI F-7000 spectrophotometer (EX Slit: 5.0 nm; EM Slit: 2.5 nm; PMT
Voltage: 400 V). CV measurements were conducted with an electrochemical workstation
(CHI660C). Compounds 6-10 were synthesized according to the previous reports [25-27].
4.2 Synthesis of bis (4-cyandiphenyl) dimethylsilane (1)
Bis(4-bromophenyl)dimethylsilane (98 mg, 0.15 mmol), 4-cyanphenylboronic acid (155 mg,
0.9 mmol), K2CO3 (248 mg,1.8 mmol), and Pd(PPh3)4 (5 mg, 0.004 mmol) in 30 mL of degassed
toluene/ethanol (10/1) were mixed and refluxed for 12 h under Ar, then filtrated. The dark filtrate
was evaporated under reduced pressure. The crude products were purified by column
chromatography (silica gel) from n-hexane/ethyl acetate as eluent to give the product as a white
solid in 95.5% yield (0.045 g). IR: (KBr pellet cm-1): 3060, 3012, 2954, 2230, 1606, 1514, 1491,
1254, 1004, 817. 1H NMR (400 MHz, CDCl3, ppm) δ: 0.66 (s, 3H, Si (CH3)2), 7.60-7.63 (d, 4H,
aromatic H), 7.67-7.77 (m, 4H, aromatic H). 13C NMR (400 MHz, CDCl3, ppm) δ: -2.47, 111.14,
118.87, 126.66, 127.72, 132.65, 134.93, 138.58, 139.94, 145.43. HRMS (FAB) calcd for
C28H22N2Si (M+H+, M+Na+, M+K+): 415.1631, 437.1450, 453.1189. Found: 415.2075, 437.1910,
453.1626. Anal. Calcd for C28H22N2Si: C, 81.12; H, 5.35; N, 6.76. Found: C, 81.08; H, 5.57; N,
6.22.
4.3 Synthesis of bis (4-cyandiphenyl) diphenylsilane (2)
The preparation procedure of 2 was similar to that of 1. Yield: 82.2%. IR: (KBr pellet cm1):
1
3054, 3015, 2960, 2227, 1605, 1486, 1427, 1111, 814. H NMR (400 MHz, CDCl3, ppm) δ:
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7.42-7.52 (m, 3H, aromatic H), 7.62-7.66 (m, 4H, aromatic H), 7.72-7.75 (m, 6H, aromatic H).
13C NMR (400 MHz, CDCl3, ppm) δ: 111.27, 118.89, 126.75, 127.79, 128.17, 130.04, 132.71,
133.46, 134.78, 136.39, 137.16, 140.35, 145.29. HRMS (FAB) calcd for C38H26N2Si (M+H3O+):
557.2049. Found: 557.1785. Anal. Calcd for C38H26N2Si: C, 84.72; H, 4.86; N, 5.20. Found: C,
84.17; H, 5.00; N, 4.91.
4.4 Synthesis of tri (4-cyandiphenyl) methylsilane (3)
The preparation procedure of 3 was similar to that of 1. Yield: 75.4%. IR: (KBr pellet cm-1):
3059, 3014, 2953, 2228, 1605, 1488, 1254, 1003, 797. 1H NMR (400 MHz, CDCl3, ppm) δ: 0.98
(s, H, Si (CH3)2), 7.63-7.66 (d, 2H, aromatic H), 7.69-7.79 (m, 6H, aromatic H). 13C NMR (400
MHz, CDCl3, ppm) δ: -3.42ꢁ111.35, 118.78, 126.80, 127.74, 132.68, 135.99, 136.09, 140.40,
145.24. 29Si NMR (400 MHz, CDCl3, ppm) δ: -10.67. Anal. Calcd for C40H27N3Si: C, 83.16; H,
4.71; N, 7.27. Found: C, 82.55; H, 5.26; N, 7.17.
4.5 Synthesis of tri (4-cyandiphenyl) phenylsilane (4)
The preparation procedure of 4 was similar to that of 1. Yield: 70.2%. IR: (KBr pellet cm-1):
3208, 3015, 2225, 1605, 1486, 1002, 813. 1H NMR (400 MHz, CDCl3, ppm) δ: (d, 4H, aromatic
13
H), (m, 4H, aromatic H). C NMR (400 MHz, CDCl3, ppm) δ: 11.38ꢁ118.77, 126.80, 127.75,
128.23, 130.16, 132.70, 133.04, 134.31, 136.32, 137.08, 140.52, 145.18. 29Si NMR (400 MHz,
CDCl3, ppm) δ: -10.68. Anal. Calcd for C45H29N3Si: C, 84.47; H, 4.57; N, 6.57. Found: C, 84.75;
H, 4.76; N, 6.28.
4.6 Synthesis of tetra (4-cyandiphenyl) silane (5)
The preparation procedure of 5 was similar to that of 1. Yield: 68.7%. IR: (KBr pellet cm-1):
1
3211, 3213, 2225, 1605, 1486, 1003, 813. H NMR (400 MHz, CDCl3, ppm) δ: 7.68-7.71 (d, H,
aromatic H), 7.73-7.79 (m, 3H, aromatic H). 13C NMR (400 MHz, CDCl3, ppm) δ: 111.48,
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118.76, 126.93, 127.76, 132.74, 133.88, 137.07, 140.08, 145.08. 29Si NMR (400 MHz, CDCl3,
ppm) δ: -14.28. Anal. Calcd for C52H32N4Si: C, 84.29; H, 4.35; N, 7.56. Found: C, 82.58; H,
4.87; N, 6.77.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (No.
21274080), the Key Natural Science Foundation of Shandong Province of China (No.
ZR2011BZ001).
Appendix. Supplementary materials
Supporting information could be found in the online version of this article, including NMR, TGA
and DSC curves of 1-5, the contour plots of the HOMO and LUMO frontier molecular orbitals of
3-5, excitation spectrum of compounds 1-5 in CH2Cl2 solution and in solid state, UV-vis
absorption spectra of 1-5 in dichloromethane solution with DPA added.
Reference
[1] H. Kai, J. Ohshita, S. Ohara, N. Nakayama, A. Kunai, I. S. Lee and Y. W. Kwak, J.
Organoment. Chem. 693 (2008) 3490-3494.
[2] Y. N. Luponosov, S. A. Ponmarenko, N. M. Surin, O. V.; Borshchev, E. A. Shumilkina and
A. M. Muzafarov, Chem. Mater. 21 (2009) 447-455.
[3] L. X. Xiao, S. J. Su, Y. Agata, H. Lan and J. J. Kido, Adv. Mater. 21 (2009)1271-1274.
[4] W. Wei, P. I. Djurovich and M. E. Thompson, Chem. Mater. 22, (2010) 1724-1731.
[5] X. M. Liu, C. He, J. Huang and J. Xu, Chem. Mater. 17 (2005) 434-441.
[6] X. M. Liu, J. Xu, X. Lu and C. He, Org. Lett. 7 (2005) 2829-2832.
[7] Q. Shen, S. Y. Ye, G. Yu, P. Lu and Y. Q. Liu, Synth. Met. 158 (2008) 1054-1058.
[8] F. K. Wang, X. H. Lu and C. B. He, J. Mater. Chem. 21(2011) 2775-2782.
10

ACCEPTED MANUSCRIPT
[9] S. Wang, W. J. Oldham Jr, R. A. Hudack and G. C. Bazan, J. Am. Chem. Soc.122 (2000)
5695-5709.
[10] L. H. Chan, R. H. Lee, C. F. Hsieh, H. C. Yeh and C. T. Chen, J. Am. Chem. Soc. 124
(2001) 6469-6479.
[11] X. M. Liu, C. He, X. T. Hao, L. W. Tan, Y. Li and K. S. Ong, Macromolecules 37(2004)
5965-5970.
[12] Y. Y. Lyu, J. Kwak, W. S. Jeon, Y. Byun, H. S. Lee, D. Kim, C. Lee and K. Char, Adv.
Funct. Mater. 19 (2009) 420-427.
[13] W. S. Han, H. J. Son, K. R. Wee, K. T. Min, S. Kwon, I. H. Suh, S. H. Choi, D. H. Jung and
S. O. Kang, J. Phys. Chem. C 113 (2009) 19686-19693; .
[14] L. X. Xiao, Z. J. Chen, B. Qu, J. X. Luo,; S. Kong, Q. H. Gong and J. J. Kido, Adv. Mater.
23 (2011) 926-952.
[15] B. K. An, D. S. Lee, J. S. Lee, Y. S. Park, H. S. Song and S. Y. Park, J. Am. Chem. Soc.
126 (2004) 10232-10233.
[16] M. S. Liu , X. Z. Jiang , S. Liu , P. Herguth , and A. K.-Y. Jen, Macromolecules 35 (2002)
3532-3538.
[17] S. Sato, K. Tajima and K. Hashimoto, Macromolecules 42 (2009) 1785-1788.
[18] J. J. You, S. L. Lai, W. M. Liu,T. W. Ng, P. F. Wang and C. S. Lee, J. Mater. Chem. 22
(2012) 8922-8929.
[19] B. Breiten, Y. L. Wu, P. D. Jarowski, J. P. Gisselbrecht, C. Boudon, M. Griesser, C. Onitsch,
G. Gescheidt, W. B. Schweizer, N. Langer, C. Lennartz and F. Diederich, Chem. Sci. 2
(2011) 88-93.
11

ACCEPTED MANUSCRIPT
[20] J. J. You, M. F. Lo,W. M. Liu, T. W. Ng, S. L. Lai, P. F. Wang and C. S. Lee, J. Mater.
Chem. 22 (2012) 5107-5113.
[21] M. S. Lin, S. J. Yang, H. W. Chang, Y. H. Huang, Y. T. Tsai, C. C. Wu, S. H. Chou, E.
Mondal and K. T. Wong, J. Mater. Chem. 22(2012) 16114-16120.
[22] R. P. Davies, R. J. Less, P. D. Lickiss, K. Robertson and A. J. P. White, Inorg. Chem. 47
(2008) 9958-9964.;
[23] G. Kwak and T. Masuda, Macromolecules 35 (2002) 4138-4242.
[24] J. Ohshita, T. Watanabe, D. Kanaya, H. Ohsaki and M. Ishikawa, Organometallics 13 (1994)
5002-5012.
[25] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J.
A. Montgomery Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, et al., Gaussian 03,
Revision D.01, Gaussian, Inc.: Wallingford, CT, 2004.
[26] M. Shimizu, K. Mochida and T. Hiyama, J. Phys. Chem. C 115 (2011) 11265-11274.
[27] T. P. Bender, J. F. Graham and J. M. Duff, Chem. Mater. 13(2001) 4105-4111.
[28] I. Kaur, W. L. Jia, R. P. Kopreski, S. Selvarasah, M. R. Dokmeci, C. Pramanik, N. E.
McGruer and G. P. Miller, J. Am. Chem. Soc. 130 (2008) 16274-16286.
[29] L. Zöphel, V. Enkelmann and K. Müllen, Org. Lett. 15 (2013) 804-807
[30] H. M. Qu and C. Y. Chi, Org. Lett. 12 (2010) 3360-3363.
[31] P. M. Beaujuge and J. R. Reynolds, Chem. Rev. 110 (2010) 268-320.
[32] Z. Q. Jiang, H. Q. Yao, Z. Y. Liu, C. L. Yang, C. Zhong, J. G. Qin, G. Yu and Y. Q. Liu,
Org. Lett. 11 (2009) 4132-4135.
[33] Y.-L. Liu, X.-Q. Ran, J.-K. Feng, A.-M. Ren and L.-Y. Zou, Aust. J. Chem. 63 (2010) 125-
130.
12

ACCEPTED MANUSCRIPT
[34] S. C. Dong, Z. Li and J. G. Qin, J. Phys. Chem. B 113 (2009) 434-441.
[35] H. Nam, B. Boury and S. Y. Park, Chem. Mater. 18 (2006) 5716-5721;
[36] X. Feng, B. Tong, J. B. Shen, J. B. Shi, T. Y. Han, L. Chen, J. G. Zhi, P. Lu, Y. G. Ma and
Y. P. Dong, J. Phys. Chem. B 114 (2010) 16731-16736.
[37] N. Malaj, O. Y. Zheng, G. Sindona and R. G.Cooks, Anal. Methods. 4 (2012) 1913-1919.
[38] M. Vuki, K. K. Shiu, M. Galik, A. M. O’Mahony and J. Wang, Analyst. 13 (2012) 3265-
3270.
[39] D. Laza, B.Nys, J. D. Kinder, A. K.-D. Mesmaeker, and C. Moucheron, J Forensic Sci. 4
(2007) 842-850.
[40] E. I. P. Ingeborg, I. Petterson, L. L. María, G. Cees, B. B. Joost and Freek Ariese, Anal.
Chem. 83 (2011) 8517-8523.
Scheme1. Synthesis routes of cyano functionalized silanes 1-5.
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Figure 1. (A) UV-vis spectra of 1-5 in CH2Cl2 solution (1×10-5 M); (B) emission spectra of 1-5 in CH2Cl2
solution (1×10-5 M, λex=278 nm); (C) emission spectra of 1-5 in solid state (λex=275 nm).
Table 1 UV-vis and Luminescent data for compounds 1-5.
UV-vis
absorption (nm)
280
ε
Excitation
(nm)
Emission
(nm)
Quantum
yields (%)
Conditions
(298 K)
CH2Cl2
compounds
(M-1.cm-1)
5.98×104
278
333
1
275
278
359, 373
333
28.8
27.9
29.7
18.2
39.8
solid state
CH2Cl2
280
282
282
282
7.65×104
1.13×104
1.06×105
1.37×105
2
3
4
5
273
388
solid state
CH2Cl2
278
333
273, 325
278
370
solid state
CH2Cl2
333
257,341
277
381
solid state
CH2Cl2
333
271
386
solid state
Table 2 Electronic Properties of Compounds 1-5
ΔE (eV) c ΔE (eV) (abs edge) d
4.73 3.86
compounds
Eox (V) a Vs Ag/Ag+
0.51
HOMO (eV) a
-4.73
LUMO (eV) b
-0.87
1
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0.84
0.83
0.82
0.50
-5.16
-5.15
-5.13
-4.66
-1.31
-1.30
-1.31
-0.84
4.74
4.75
4.74
4.74
3.85
3.85
3.82
3.82
2
3
4
5
a Measured in CH2Cl2 at room temperature in the presence of Bu4NClO4 (0.1 M) as supporting electrolyte at a
b
scan rate of 100 mV/s using Pt as the working electrode and Ag/AgCl as the reference electrode. Calculated
from EHOMO (CV) and ꢀE (abs edge). c Calculated by DFT/B3LYP/6-31G (d) using Gaussian. d Estimated from
the absorption edge.
Figure 2. HOMO and LUMO distributions obtained from DFT calculations of compounds 1and 2.
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Figure 3 Fluorescence emission spectra (left) of 1 (10 ꢁM) upon the addition of DPA (0.01mol/L in methanol)
in THF solution (λex = 278 nm) and obtained Stern–Volmer plot (right) with DPA (0-70ꢁM).
Figure 4 Fluorescence emission spectra (left) of 2 (10 ꢁM) upon the addition of DPA (0.01mol/L in methanol)
in THF solution (λex = 278 nm) and obtained Stern–Volmer plot (right) with DPA (0-70ꢁM).
Table 3 Linear fitting data of 1-5 for the fluorescent response to DPA
1
2
3
4
5
concentration range of DPA (ꢁM)
correlation coefficient R
binding constants Ksv (106 M-1)
0-70
0.9977
1.96
0-70
0.9975
1.19
0-50
0.9969
1.99
0-50
0.9941
1.10
0-70
0.9980
1.04
fluorescence quenching percentage
92.47%
92.91%
93.86%
91.63%
85.61%
with 150ꢁM DPA
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Figure 5 UV absorption spectra (left) of 1 (10 ꢁM) upon the addition of DPA (0.01mol/L in methanol) in THF
solution and obtained Stern–Volmer plot (right) with DPA (0-110ꢁM).
Table 4 Linear fitting data of 1-5 for the UV absorption response to DPA
1
2
3
4
5
concentration range of DPA (ꢁM)
correlation coefficient R
binding constants Ksv (104 M-1)
0-110
0.9930
4.90
0-90
0.9890
4.64
0-40
0.9887
1.93
0-70
0.9915
1.73
0-50
0.9805
3.13
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Highlights
ꢀ
We synthesize a new series of silicon-centered cyano functionalized silanes.
ꢀ They all display high thermal stability and strong blue fluorescence emission.
They all exhibit the linear fluorescent quenching response to diphenylamine.
ꢀ

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Supporting information for
New cyano functionalized silanes： Synthesis, characterization and
diphenylamine detection
Linlin Wang, DengxuWang, Hua Wang, Lei Xue, and Shengyu Feng*
Key Laboratory of Special Functional Aggregated Materials, Ministry of Education; School of
Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, PR China
Corresponding author: Shengyu Feng
Email address: fsy@sdu.edu.cn

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Figure S1. 1H NMR spectrum of 1 in chloroform-d
Figure S2. 13C NMR spectrum of 1 in chloroform-d

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Figure S3. 1H NMR spectrum of 2 in chloroform-d
Figure S4. 13C NMR spectrum of 2 in chloroform-d

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Figure S5. 29Si NMR spectrum of 2 in chloroform-d
Figure S6. 1H NMR spectrum of 3 in chloroform-d

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Figure S7. 13C NMR spectrum of 3 in chloroform-d
Figure S8. 29Si NMR spectrum of 3 in chloroform-d

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Figure S9. 1H NMR spectrum of 4 in chloroform-d
Figure S10. 13C NMR spectrum of 4 in chloroform-d

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Figure S11. 29Si NMR spectrum of 4 in chloroform-d
Figure S12. 1H NMR spectrum of 5 in chloroform-d

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Figure S13. 13C NMR spectrum of 5 in chloroform-d
Figure S14. 29Si NMR spectrum of 5 in chloroform-d

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Figure S15. TGA curves of compounds 1-5.
Figure S16. DSC curves of compounds 1-5.