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Ultrafast Through-Space Electronic Energy Transfer in Molecular Dyads Built around Dynamic Spacer Units

Lookup NU author(s): Dr Raymond Ziessel, Patrycja Stachelek, 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.

Publication metadata

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

Year: 2018

Volume: 122

Issue: 18

Pages: 4457-4447

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


DOI: 10.1021/acs.jpca.8b02415


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