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Competition between the Heavy Atom Effect and Vibronic Coupling in Donor-Bridge-Acceptor Organometallics

Lookup NU author(s): Dr Julien EngORCiD, Stuart Thompson, Professor Thomas Penfold



This is the authors' accepted manuscript of an article that has been published in its final definitive form by Royal Society of Chemistry, 2020.

For re-use rights please refer to the publisher's terms and conditions.


The excited state properties and intersystem crossing dynamics of a series of donor-bridge- acceptor carbene metal-amides based upon the coinage metals Cu (Cu-Cz), Ag (Ag-Cz), Au (Au-Cz), are investigated using quantum dynamics simulations and supported by photophysical characterisation. The simulated intersystem rates are consistent with experimental observations making it possible to provide a detailed interpretation of the excited state dynamics which ultimately control their functional properties. It is demonstrated that for all complexes there is a competition between the direct intersystem crossing occurring between the 1CT and 3CT states and indirect pathways which couple to an intermediate locally excited ππ triplet state (3LE) on either the donor or acceptor ligands. The energy of the 3LE states decreases as the size of the metal decreases meaning that the indirect pathway plays an increasingly important role for the lighter metals. Importantly whenever the direct pathway is efficient, the presence of indirect path- ways is detrimental to the overall rate of ISC as they provide a slower alternative pathway. Our results provide a detailed insight into the mechanism of intersystem crossing in these complexes and will greatly facilitate the design of new higher performing molecules.

Publication metadata

Author(s): Eng J, Thompson S, Goodwin H, Credgington D, Penfold TJ

Publication type: Article

Publication status: Published

Journal: Physical Chemistry Chemical Physics

Year: 2020

Volume: 22

Issue: 8

Pages: 4659-4667

Print publication date: 28/02/2020

Online publication date: 06/02/2020

Acceptance date: 06/02/2020

Date deposited: 06/02/2020

ISSN (print): 1463-9076

ISSN (electronic): 1463-9084

Publisher: Royal Society of Chemistry


DOI: 10.1039/C9CP06999B


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