Lookup NU author(s): Dr Raymond Ziessel,
Emeritus Professor Anthony Harriman
This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2018.
For re-use rights please refer to the publisher's terms and conditions.
A pair of complementary molecular dyads have been synthesized around a 1,2-diaminocyclohexyl spacer that itself undergoes ring inversion. Despite these conformational exchange processes, the donor and acceptor occupy quite restricted spatial regions, and they are not interchangeable. The donor and acceptor pair comprise disparate boron dipyrromethene dyes selected to display favorable electronic energy transfer (EET). Steady-state emission spectroscopy confirms that through-space EET from donor to acceptor is almost quantitative, aided by the relatively short separations. Ultrafast time-resolved fluorescence spectroscopy has allowed determination of the rates of EET for both dyads. Surprisingly, in view of the close proximity of donor and acceptor (center-to-center separations less than 20 A), the EET dynamics are well-accounted for in terms of the computed molecular conformations and conventional Forster theory. One dyad appears as a single family of conformations, but EET for the second dyad corresponds to dual-exponential kinetics. In this latter case, an intramolecular hydrogen bond helps stabilize an open geometry, wherein EET is relatively slow.
Author(s): Ziessel R, Stachelek P, Harriman A, Hedley GJ, Roland T, Ruseckas A, Samuel IDW
Publication type: Article
Publication status: Published
Journal: The Journal of Physical Chemistry A
Print publication date: 10/05/2018
Online publication date: 17/04/2018
Acceptance date: 17/04/2018
Date deposited: 05/06/2018
ISSN (print): 1089-5639
Publisher: American Chemical Society
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