Intra- vs Intermolecular Photoinduced Electron Transfer Reactions of a Macrocyclic Donor-Acceptor Dyad

Moore, Evan G.; Bernhardt, Paul V.; Fürstenberg, Alexandre; Riley, Mark J.; Vauthey, Eric

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Title		Intra- vs Intermolecular Photoinduced Electron Transfer Reactions of a Macrocyclic Donor-Acceptor Dyad
Authors		Moore, Evan G. Bernhardt, Paul V. Fürstenberg, Alexandre Riley, Mark J. Vauthey, Eric
Published in		Journal of Physical Chemistry. A. 2005, vol. 109, no. 51, p. 11715-11723
Abstract		The synthesis, structural characterization, and photophysical behavior of a 14-membered tetraazamacrocycle with pendant 4-dimethylaminobenzyl (DMAB) and 9-anthracenylmethyl groups is reported (L3, 6-((9-anthracenylmethyl)amino)-trans-6,13-dimethyl-13-((4-dimethylaminobenzyl)amino)-1,4,8,11-tetraazacyclotetradecane). In its free base form, this compound displays rapid intramolecular photoinduced electron transfer (PET) quenching of the anthracene emission, with both the secondary amines and the DMAB group capable of acting as electron donors. When complexed with Zn(II), the characteristic fluorescence of the anthracene chromophore is restored as the former of these pathways is deactivated by coordination. Importantly, it is shown that the DMAB group, which remains uncoordinated and PET active, acts only very weakly to quench emission, by comparison to the behavior of a model Zn complex lacking the pendant DMAB group, [ZnL2]2+ (Chart 1). By contrast, Stern−Volmer analysis of intermolecular quenching of [ZnL2]2+ by N,N-dimethylaniline (DMA) has shown that this reaction is diffusion limited. Hence, the pivotal role of the bridge in influencing intramolecular PET is highlighted.
Identifiers		DOI: 10.1021/jp0547414
Full text		Article (Published version) - Free access Other version: http://pubs.acs.org/cgi-bin/article.cgi/jpcafh/2005/109/i51/pdf/jp0547414.pdf
Structures		Faculté des sciences / Section de chimie et biochimie / Département de chimie physique
Research group		Groupe Vauthey
Citation (ISO format)		MOORE, Evan G. et al. Intra- vs Intermolecular Photoinduced Electron Transfer Reactions of a Macrocyclic Donor-Acceptor Dyad. In: Journal of Physical Chemistry. A, 2005, vol. 109, n° 51, p. 11715-11723. https://archive-ouverte.unige.ch/unige:3263