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External-Stimuli Responsive Photophysics and Liquid Crystal Properties of Self-Assembled ``Phosphole-Lipids''

TitleExternal-Stimuli Responsive Photophysics and Liquid Crystal Properties of Self-Assembled ``Phosphole-Lipids''
Publication TypeJournal Article
Year of Publication2011
AuthorsRen, Y, Kan, WHay, Henderson, MA, Bomben, PG, Berlinguette, CP, Thangadurai, V, Baumgartner, T
JournalJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume133
Pagination17014-17026
Date PublishedOCT 26
ISSN0002-7863
Abstract

A series of new amphiphilic phosphonium materials that combine the electronic features of phospholes with self-assembly features of lipids were synthesized. Variable concentration/temperature and 2D NMR studies suggested that the systems undergo intramolecular conformation changes between a ``closed{''} and ``open{''} form that are triggered by intermolecular interactions. The amphiphilic features of the phospholium species also induce liquid crystalline and soft crystal phase behavior in the solid state, which was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature powder X-ray diffraction (VT-PXRD). The studies revealed that both conjugated backbones and counteranions work together to organize the systems into different morphologies (liquid crystal/soft crystal). Dithieno{[}3,2-b:2',3'-d]phosphole-based compounds exhibit enhanced emission in the solid state and at low temperature in solution due to aggregation-induced enhanced emission (AIEE). Photoinduced electron transfer (PET) induced via the alkoxybenzyl group at the phosphonium center in the fused-ring systems can be effectively suppressed through intermolecular charge transfer (ICT) processes within the main scaffold of a nonfused system, which was confirmed by static and dynamic fluorescence spectroscopy. The dynamic features of these new materials also endow the systems with external-stimuli responsive photophysical properties that can be triggered by temperature and/or mechanical forces.

DOI10.1021/ja206784f