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High-Efficiency Iron Photosensitizer Explained With Quantum Wavepacket Dynamics

Lookup NU author(s): Professor Thomas Penfold

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Abstract

Fe(II) complexes have long been assumed unsuitable as photosensitisers because of their low-lying non-emissive metal centred (MC) states, which inhibit electron transfer. Herein, we describe the excited state relaxation of a novel Fe(II) complex that incor- porates N-heterocyclic carbene ligands designed to destabilise the MC states. Using rst principles quantum nuclear wavepacket simulations we achieve a detailed under- standing of the photoexcited decay mechanism, demonstrating that it is dominated by an ultrafast intersystem crossing from 1MLCT-3MLCT proceeded by slower kinetics associated with the conversion into the 3MC states. The slowest component of the 3MLCT decay, important in the context of photosensitisers, are much longer than re- lated Fe(II) complexes because the population transfer to the 3MC states occurs in a region of the potential where the energy gap between the 3MLCT and 3MC states is large, making the population transfer inecient.

Publication metadata

Author(s): Pápai M, Vankó G, Rozgonyi T, Penfold T

Publication type: Article

Publication status: Published

Journal: Journal of Physical Chemistry Letters

Year: 2016

Volume: 7

Pages: 2009-2014

Online publication date: 11/05/2016

Acceptance date: 11/05/2016

Date deposited: 13/05/2016

ISSN (electronic): 1948-7185

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/acs.jpclett.6b00711

DOI: 10.1021/acs.jpclett.6b00711

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