NDLI: Charge transfer through cross-hyperconjugated <i>versus</i> cross-π-conjugated bridges: an intervalence charge transfer study

Content Provider	Royal Society of Chemistry (RSC)
Author	Markle, Todd F. Hammarström, Leif Ottosson, Henrik Jorner, Kjell Emanuelsson, Rikard Göransson, Erik
Copyright Year	2013
Abstract	Recently there has been much interest in electron transfer and transport through cross-conjugated molecules as interesting test cases for the interplay between molecular and electronic structure as well as potential motifs in the design of new compounds for molecular electronics. Herein we expand on this concept and present the synthesis and characterization of a series of four organic mixed-valence dyads to probe the effect of the bridge structure on the electronic coupling. The electronic coupling between two triarylamine units could be mediated either by cross-hyperconjugation through a saturated ER2 bridge (E = C or Si, R = alkyl or silyl group), or via a cross-conjugated π-system. The aim of the study is to compare the electron transfer through the various saturated bridges to that of a cross-π-conjugated bridge. The electronic coupling in these mixed-valence compounds was determined by analysis of intervalence charge transfer bands, and was found to be in the range of 100–400 cm−1. A complementary DFT and TD-DFT study indicated that the electronic coupling in the dyads with saturated ER2 segments is highly conformer dependant. Furthermore, the calculations showed that two types of interactions contribute to the electronic coupling; a through-bond cross-(hyper)conjugation mechanism and a through-space mechanism. Taken together, these findings suggest the possibility for new architectures for molecular electronics applications utilizing cross-hyperconjugation through properly selected saturated segments which have comparable electron transfer characteristics as regular cross-π-conjugated molecules.
Starting Page	3522
Ending Page	3532
Page Count	11
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	4
Issue Number	9
Journal	Chemical Science
DOI	10.1039/c3sc50844g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Molecular electronics Alkyl Interplay Entertainment
Content Type	Text
Resource Type	Article
Subject	Chemistry

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