Directly coupled versus spectator linkers on diimine ptii acetylides—change the structure, keep the function

Journal article


Archer, Stuart A., Keane, Theo, Delor, Milan, Bevon, Elizabeth, Auty, Alexander J., Chekulaev, Dimitri, Sazanovich, Igor V., Towrie, Michael, Meijer, Anthony J. H. M. and Weinstein, Julia A. 2017. Directly coupled versus spectator linkers on diimine ptii acetylides—change the structure, keep the function. Chemistry a European Journal.. 23 (72), pp. 18239-18251. https://doi.org/10.1002/chem.201703989
AuthorsArcher, Stuart A., Keane, Theo, Delor, Milan, Bevon, Elizabeth, Auty, Alexander J., Chekulaev, Dimitri, Sazanovich, Igor V., Towrie, Michael, Meijer, Anthony J. H. M. and Weinstein, Julia A.
Abstract

Modification of light‐harvesting units with anchoring groups for surface attachment often compromises light‐harnessing properties. Herein, a series of [donor–acceptor–anchor] platinum(II) diimine (bis‐)acetylides was developed in order to systematically compare the effect of conjugated versus electronically decoupled modes of attachment of protected anchoring groups on the photophysical properties of light‐harvesting units. The first examples of “decoupled” phosphonate diimine PtII complexes are reported, and their properties are compared and contrasted to those of carboxylate analogues studied by a diversity of methods. Ultrafast time‐resolved IR and transient absorption spectroscopy revealed that all complexes have a charge‐transfer (CT) lowest excited state with lifetimes between 2 and 14 ns. Vibrational signatures and dynamics of CT states were identified; the assignment of electronic states and their vibrational origin was aided by TDDFT calculations. Ultrafast energy redistribution accompanied by structural changes was directly captured in the CT states. A significant difference between the structures of the electronic ground and CT excited states, as well as differences in the structural reorganisation in the complexes bearing directly attached or electronically decoupled anchoring groups, was discovered. This work demonstrates that decoupling of the anchoring group from the light‐harvesting core by a saturated spacer is an easy approach to combine surface attachment with high reduction potential and ten times longer lifetime of the CT excited state of the light‐absorbing unit, and retain electron‐transfer photoreactivity essential for light‐harvesting applications.

Keywordslight harnessing
Year2017
JournalChemistry a European Journal.
Journal citation23 (72), pp. 18239-18251
PublisherWiley
ISSN09476539
Digital Object Identifier (DOI)https://doi.org/10.1002/chem.201703989
Web address (URL)http://hdl.handle.net/10545/623423
hdl:10545/623423
Publication dates27 Dec 2017
Publication process dates
Deposited28 Jan 2019, 19:13
Accepted13 Oct 2017
ContributorsUniversity of Sheffield, Rutherford Appleton Laboratory, Didcot, University of California, Berkeley and Moscow Lomonosov State University, Russia
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