Novel Polysiloxanes Containing Sulfonyl Chromophores as Side Chains

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1 , ACTA CHIMICA SINICA Vol 62, 2004 No 4, a a a a Ξ, a b b Ξ ( a ) ( b ), -, (SHG) d pm/ V,,,, Novel Polysiloxanes Containing Sulfonyl Chromophores as Side Chains LI, Zhen a HUANG, Cheng a HUA, Jian2Li a HUANG, Bing a QIN, Jin2Gui Ξ, a YANG, Zhou b YE, Cheng b ( a Department of Chemistry, Wuhan University, Wuhan ) ( b Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing ) Abstract A new synthetic strategy was developed to prepare polysiloxanes with indole2based chromophore side chains, in which sulfonyl groups act as the acceptor groups Molecular structural characterization for the polymers was presented by 1 H NMR, IR and UV2vis spectra and differential scanning calorimetry (DSC) This synthetic method is simple, and the purification is easy The poled film of 2 and 3 reveals a resonant d 33 value of 21 and 17 pm/ V respectively by second harmonic generation ( SHG ) measurements Keywords post functionalization, synthesis, indole, sulfonyl group, second2order optical nonlinearity (NLO),, (, ),,,,,Park [4] [5,6],, d pm/ V,,,, Park,,, [1 3] Ξ E2mail : edu cn Received July 7, 2003 ; revised September 19, 2003 ; accepted October 28, 2003 (973) (No 2003ABAO74) (No 2003X107)

2 No 4 : 411,,,, 5 8 g ( / 40 Pa),, [ 86 % 1 H NMR (300 MHz, CDCl 3 ) : 7 65 ( d, 1H, ArH), p (SO 2 R) = , p (NO 2 ) = ], (m, 4H, ArH), 6 54 (d, 1H, ArH), [7], (m, 1H, CCH C), (m, 2H, CH 2 C), 4 70, (t, 2H, CH 2 ), (12 ) (1), Schlenk, (0 192, ( g, 3 2 mmol) N2 (1 25 g, 7 9 mmol) ), (5 ml), h,,, 2 h,,,,,,, (0 61 g, 88 %), mg 1, 30 ml, 1 1 1, 1 h,, Varian Mercury 300,, ;,,,, NICOLET2170SX Perkin Elmer instruments Spectrum One,,, ; 110 mg - Shimadzu Tencor , ; Rigaku Thermoflex DSC8131 Perkin2Elmer 7 series Thermal Analyzer, mg 66 ml, 180 mg, 20 / min 1 3 N2 (NMP) [8 ] 4 % ( ) [9 ], 1 2 (syringe filter), ( spin2coating) ITO, r/ min, 40 s, h, (2 79 g, mol) 9 90 g 40 % ( mol), 0 5, 0 51 m 4 ml (1 04 g, mol), ( d h, 33 ) (SHG),, 4105 g, 95 %,, [11 ] N2 [10], 100 ml (12 g, 21 4 mmol) N, N2 (50 ml), 20 min, (5 0 g, 42 6 mmol) h, 32 (6 2 3, ml, 75 mmol) 10 ml N, N2,,, h, 1 L, 1 2 ml NMP, 0, 63 mg, 8 h K 2 CO 3, 2 (Scheme 1),,,

3 412 Vol 62, 2004, ( 3 2 ),, 1,,,, ,, , ,, , [12,13] 2 3 1, 1 25 %,, 2, Si H, Figure 1 1 H NMR spectrum of polysiloxane 1 Scheme nm 2 2, 1 3,, cm - 1, 2 3 C H, cm nm Si O Si,1260, 801 cm - 1 Si CH 3, 30 1, 2 3, 1128 cm nm,, 2 3,,, nm cm - 1,,,,1,22,DMF, DMSO, 1 1, nm ; 21,

4 No 4 : 413 ( ), [1,2], ( ),,,,, 2 2 ( 3 TMS, # solvent) Figure 2 1 H NMR spectrum of polysiloxane 2 ( 3 TMS, # solvent) Figure 3 UV2vis spectra of polysiloxanes 1 3 References 1 Moerner, W E ; Jepsen, A G ; Thompson, C L Ann Rev Mater Sci 1997, 27, Moerner, W E ; Silence, S M Chem Rev 1994, 94, Ye, C In Organic Solids, Eds : Zhu, D B ; Wang, F S, Shanghai Science & Technology Press, Shanghai, 1999, p 181 (,, :,,,, 1999, p 181 ) 4 Moon, H ; Hwang, J ; Kim, N ; Park, S Y Macromolecules 2000, 33, (a) Zhang, Y ; Wada, T ; Wang, L ; Aoyama, T ; Sasabe, H Chem Commun 1996, 2325 (b) Zhang, Y ; Wada, T ; Wang, L ; Sasaba, H Macromol Chem Phys 1996, 197, Ho, M S ; Barrett, C ; Paterson, J ; Esteghamatian, M ; Natansohn, A ; Rochon, P Macromolecules 1996, 29, Abraham, U ; Graig, S W ; Werner, K ; Douglas, R R ; David, J W ; Laura, H J Am Chem Soc 1990, 112,, Doyle, J R ; Jonassen, H B J Am Chem Soc 1956, ( d 33 ) 78, 396 (SHG) 9 Courtin, A Helv Chim Acta 1983, 66, 1046, 10 Harry, H G ; Harlan, B F US , 1949 [ Chem,, Abstr 1949, 43, 4302e ] 40, Zhu, P W ; Wang, P ; Zhao, K S ; Ye, C High Technol d pm/ V, Commun 1999, 9, 35 (in Chinese) (,,,,, 1999, 9, 35 ) 12 Li, Z ; Qin, J ; Tang, H ; Liu, Y J Appl Polym Sci , 89, 2989, [4] 13 Li, Z ; Qin, J ; Li, S ; Ye, C ; Luo, J ; Cao, Y, Macromolecules 2002, 35, , (A LI, L T ; FAN, Y Y ),

5 Graphical Abstract Vol 62, 2004 Preparation and Characterization of A New p2 Allylcalix[ 4] arene2bonded Silica Gel Station2 ary Phase for High2Performance Liquid Chro2 matography LI, Wen2Zhi ; WANG, Xia ; DOU, Jian2Min ; MA, Chun2Lin ; CHEN, Li2Ren ; LI, Yong2Min Acta Chimica Sinica 2004, 62 (4), 405 5,11, 17, 232Tetraallyl225, 26, 27, 282tetra2( (phenylethaminocarbonyl) methoxy) calix [ 4 ] arene2bonded stationary phase shows an excellent separation of positional isomers with mobile phase of methanol2water and represents a predominantly reversed2phase character Novel Polysiloxanes Containing Sulfonyl Chro2 mophores as Side Chains LI, Zhen ; HUANG, Cheng ; HUA, Jian2Li ; HUANG, Bing ; QIN, Jin2Gui ; YANG, Zhou ; YE, Cheng Acta Chimica Sinica 2004, 62 (4), 410 A new synthetic strategy was developed to prepare polysiloxanes with indole2based chro2 mophore side chains, in which sulfonyl groups act as the acceptor groups This synthetic method is very simple, and the purification is very easy The resultant polysiloxanes exhibit relatively high second order nonlinear optical values Electrochemical Synthesis of Tin Complexes and Preparation of Nano2sized SnO 2 ZHOU, Xing2Fu ; ZHAO, Jun2Feng ; CHU, Dao2 Bao Acta Chimica Sinica 2004, 62 (4), 414 Tin complexes of Sn(OEt) 4, Sn(OBu) 4, Sn(OCH 2 CH 2 OCH 3 ) 4, Sn(OEt) 2 (acac) 2, Sn(OBu) 2 (acac) 2 and Sn(OCH 2 CH 2 OCH 3 ) 2 (acac) 2 were directly electrochemically synthe2 sized by using tin metal as sacrificial anode in non2aqueous media Nano2sized SnO 2 was pre2 pared by direct hydrolysis of the electrolyte solution containing Sn(OEt) 2 (acac) 2 precursor