Symmetry Effects in Photoinduced Electron Transfer in Chlorin-Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region.
artificial photosynthesis
chlorin
electron transfer
quinone
symmetry
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
18 Dec 2020
18 Dec 2020
Historique:
received:
05
06
2020
pubmed:
7
7
2020
medline:
7
7
2020
entrez:
7
7
2020
Statut:
ppublish
Résumé
In donor-acceptor dyads undergoing photoinduced electron transfer (PET), a direction or pathway for electron movement is usually dictated by the redox properties and the separation distance between the donor and acceptor subunits, while the effect of symmetry is less recognized. We have designed and synthesized two isomeric donor-acceptor assemblies in which electronic coupling between donor and acceptor is altered by the orbital symmetry control with the reorganization energy and charge transfer exothermicity being kept unchanged. Analysis of the optical absorption and luminescence spectra, supported by the DFT and TD-DFT calculations, showed that PET in these assemblies corresponds to the Marcus inverted region (MIR) and has larger rate for isomer with weaker electronic coupling. This surprising observation provides the first experimental evidence for theoretically predicted adiabatic suppression of PET in MIR, which unambiguously controlled solely by symmetry.
Identifiants
pubmed: 32628802
doi: 10.1002/chem.202002736
pmc: PMC7839475
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
17120-17127Subventions
Organisme : Deutsche Forschungsgemeinschaft
ID : MO 274/10
Organisme : NSF XSEDE
ID : TG-CHE170004
Informations de copyright
© 2020 The Authors. Published by Wiley-VCH GmbH.
Références
J Am Chem Soc. 2009 Nov 11;131(44):16292-302
pubmed: 19831383
Angew Chem Int Ed Engl. 2009;48(14):2474-99
pubmed: 19294671
Chemistry. 2020 Dec 18;26(71):17120-17127
pubmed: 32628802
Chem Soc Rev. 2012 Feb 7;41(3):1075-87
pubmed: 22105355
J Phys Chem C Nanomater Interfaces. 2014 Sep 18;118(37):21400-21408
pubmed: 25264475
J Am Chem Soc. 2005 Nov 30;127(47):16348-9
pubmed: 16305193
J Phys Chem Lett. 2016 Aug 4;7(15):2915-20
pubmed: 27409718
J Phys Chem A. 2007 Mar 22;111(11):2047-53
pubmed: 17311366
J Am Chem Soc. 2015 Dec 2;137(47):14999-5006
pubmed: 26545043
Annu Rev Phys Chem. 2007;58:143-84
pubmed: 17059368
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14468-72
pubmed: 26425818
Chem Rev. 2011 Nov 9;111(11):7260-314
pubmed: 21740071
J Am Chem Soc. 2002 Apr 24;124(16):4212-3
pubmed: 11960441
Chem Commun (Camb). 2010 Oct 14;46(38):7090-108
pubmed: 20835465
Acc Chem Res. 2001 Feb;34(2):159-70
pubmed: 11263874
Chemistry. 2015 Jan 7;21(2):590-600
pubmed: 25381747
Chemistry. 2007;13(23):6595-604
pubmed: 17516607
Angew Chem Int Ed Engl. 2017 Jan 2;56(1):266-269
pubmed: 27897375
J Am Chem Soc. 2001 Oct 31;123(43):10676-83
pubmed: 11673999