Cyanine-like dyes with large bond-length alternation.

TitleCyanine-like dyes with large bond-length alternation.
Publication TypeJournal Article
Year of Publication2013
AuthorsThorley KJ, Hales JM, Kim H, Ohira S, Brédas J-L, Perry JW, Anderson HL
JournalChemistry (Weinheim an der Bergstrasse, Germany)
Volume19
Issue31
Pagination10370-7
Date Published2013 Jul 29
Abstract

Herein, the synthesis and properties of alkyne-bridged carbocations, which are analogous in structure to cyanine dyes, are reported. An alkene-bridged dye, linked at the third position of the indole, was also synthesized as a reference compound. These new carbocations are stable under ambient conditions, allowing characterization by UV/Vis and NMR ((1)H and (13)C) spectroscopies. These techniques revealed a large degree of delocalization of the positive charge, similar to a previously reported porphyrin carbocation. The linear and nonlinear optical properties are compared with cyanine dyes and triarylmethyl cations, to investigate the effects of the bond-length alternation and the overall molecular geometry. The value of Re(γ), the real part of the third-order microscopic polarizability, of -1.3×10(-33)  esu for the alkyne-linked cation is comparable to that of a cyanine dye of similar length. Nondegenerate two-photon absorption spectra showed that the alkene-bridged dye exhibited characteristics of cyanines, whereas the alkyne-bridged dye is reminiscent of octupolar chromophores, such as the triarylmethyl carbocation brilliant green. Such attributes were confirmed and rationalized by quantum chemical calculations.

DOI10.1371/journal.pone.0075831
Alternate JournalChemistry