Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad

Moore, E. G., Bernhardt, P. V., Furstenberg, A., Riley, M. J. and Vauthey, E. (2005) Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad. Journal of Physical Chemistry A, 109 51: 11715-11723. doi:10.1021/jp0547414


Author Moore, E. G.
Bernhardt, P. V.
Furstenberg, A.
Riley, M. J.
Vauthey, E.
Title Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad
Journal name Journal of Physical Chemistry A   Check publisher's open access policy
ISSN 1089-5639
Publication date 2005
Sub-type Article (original research)
DOI 10.1021/jp0547414
Volume 109
Issue 51
Start page 11715
End page 11723
Total pages 9
Place of publication Washington, DC, U.S.A.
Publisher American Chemical Society
Collection year 2005
Language eng
Subject C1
250201 Transition Metal Chemistry
780103 Chemical sciences
Abstract The synthesis, structural characterization, and photophysical behavior of a 14-membered tetraazamacrocycle with pendant 4-dimethylaminobenzyl (DMAB) and 9-anthracenylmethyl groups is reported (L-3, 6-((9-anthracenylmethyl)amino)-trans-6,13-dimethyl-13-((4-dimethylaminobenzyl)amino)-1,4,8,11-tetraaza-cyclotetradecane). 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.
Keyword Chemistry, physical
Physics, atomic, molecular and chemical
Charge-recombination
Energy transfer
Excited-state
Ion-pairs
Anthracene
Complexes
Cyclam
N,n-dimethylaniline
Carboxylates
Derivatives
Q-Index Code C1

 
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Created: Wed, 15 Aug 2007, 06:38:45 EST