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Supramolecular template-directed synthesis of perfect phenelenediimino-bridged ladderlike polyphenylsiloxanes

文献类型:期刊论文

作者Zhang, TY; Deng, KL; Zhang, PP; Xie, P; Zhang, RB
刊名Chemistry-a european journal
出版日期2006-04-14
卷号12期号:13页码:3630-3635
关键词Hydrolysis Ladder superstructure Self-assembly Silicon Supramolecular chemistry
ISSN号0947-6539
DOI10.1002/chem.200501447
通讯作者Zhang, rb(zhagrb@iccas.ac.cn)
英文摘要A template synthesis of the soluble, high molecular weight (m,,), and perfect p-phenylenedimino (p-pda)-bridged ladderlike polyphenylsiloxane (plps) is reported. first, n,n'-bis(phenyldichlorosilyl)-p-pda monomers were self-assembled into a perfect ladder superstructure (ls) by concerted interaction of aromatic pi-pi stacking and hydrogen bonding. then the ls underwent a novel stoichiometric hydrolysis/dehydrochlorination-condensation reaction instead of the usual hydrolysis/dehydration-condensation reaction, leading to the plps. the perfect ladder structures of both the plps and, in particular, the unstable supramolecular ls were confirmed as follows. 1) there are two bragg peaks in solid and/or solution x-ray diffraction (xrd) spectra representing the ladder width (w) and ladder thickness (t); these peaks were consistent with those calculated by molecular simulation. 2) both the plps and ls have extremely sharp absorption peaks with small half-peak widths (delta(1/2) < 0.3 ppm) in si-29 nmr spectra, suggesting the presence of the perfect ladder structure for plps and ls. 3) moreover, no noticeable absorption peaks for the si-oh and nh2 groups were observed in ftir and si-29 nmr spectra, indicating that the si-n bond of the equivalent to si-nh-c6h4-nh-si equivalent to ladder rung of plps and ls is not cleaved. 4) both plps and ls show similar emission peaks (in fluorescence spectroscopy) attributed to the excimer formed by face-to face pi-pi stacking of phenyl groups along the ladder chain rather than a branched direction. 5) differential scanning calorimetry (dsc) measurements indicate a high glass temperature (t-g=176.4 degrees c) for plps. as circumstantial evidence, this result further indicates very high stiffness of plpss ladder backbone as compared with flexible single-chain polyphenylmethyl-siloxane with a low t-g = -69.4 degrees c.
WOS关键词STEPWISE COUPLING POLYMERIZATION ; INTRAMOLECULAR EXCIMER FORMATION ; POLYMETHYLSILOXANE ; FLUORESCENCE ; POLYMERS ; POLY(PHENYLSILSESQUIOXANE) ; PHENYLSILSESQUIOXANE ; SILSESQUIOXANES
WOS研究方向Chemistry
WOS类目Chemistry, Multidisciplinary
语种英语
WOS记录号WOS:000237177800021
出版者WILEY-V C H VERLAG GMBH
URI标识http://www.irgrid.ac.cn/handle/1471x/2378845
专题中国科学院大学
通讯作者Zhang, RB
作者单位1.Chinese Acad Sci, Inst Chem, State Key Lab Polymer Phys & Chem, Joint Lab Polymer Sci & Mat, Beijing 100080, Peoples R China
2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China
3.Beijing Univ Chem Technol, Beijing 100029, Peoples R China
推荐引用方式
GB/T 7714
Zhang, TY,Deng, KL,Zhang, PP,et al. Supramolecular template-directed synthesis of perfect phenelenediimino-bridged ladderlike polyphenylsiloxanes[J]. Chemistry-a european journal,2006,12(13):3630-3635.
APA Zhang, TY,Deng, KL,Zhang, PP,Xie, P,&Zhang, RB.(2006).Supramolecular template-directed synthesis of perfect phenelenediimino-bridged ladderlike polyphenylsiloxanes.Chemistry-a european journal,12(13),3630-3635.
MLA Zhang, TY,et al."Supramolecular template-directed synthesis of perfect phenelenediimino-bridged ladderlike polyphenylsiloxanes".Chemistry-a european journal 12.13(2006):3630-3635.

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来源:中国科学院大学

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