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Orbital-free photophysical descriptors to predict directional excitations in metal-based photosensitizers

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Abstract

The development of dye-sensitized solar cells, metalloenzyme photocatalysis or biological labeling heavily relies on the design of metal-based photosensitizes with directional excitations. Directionality is most often predicted by characterizing the excitations manually via canonical frontier orbitals. Although widespread, this traditional approach is, at the very least, cumbersome and subject to personal bias, as well as limited in many cases. Here, we demonstrate how two orbital-free photophysical descriptors allow an easy and straightforward quantification of the degree of directionality in electron excitations using chemical fragments. As proof of concept we scrutinize the effect of 22 chemical modifications on the archetype [Ru(bpy)3]2+ with a new descriptor coined “substituent-induced exciton localization” (SIEL), together with the concept of “excited-electron delocalization length” (EEDLn). Applied to quantum ensembles of initially excited singlet and the relaxed triplet metal-to-ligand charge-transfer states, the SIEL descriptor allows quantifying how much and whereto the exciton is promoted, as well as anticipating the effect of single modifications, e.g. on C-4 atoms of bpy units of [Ru(bpy)3]2+. The general applicability of SIEL and EEDLn is further established by rationalizing experimental trends through quantification of the directionality of the photoexcitation. We thus demonstrate that SIEL and EEDL descriptors can be synergistically employed to design improved photosensitizers with highly directional and localized electron-transfer transitions.

Graphical abstract: Orbital-free photophysical descriptors to predict directional excitations in metal-based photosensitizers

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Supplementary files

Article information


Submitted
22 Mar 2020
Accepted
14 May 2020
First published
15 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Orbital-free photophysical descriptors to predict directional excitations in metal-based photosensitizers

P. A. Sánchez-Murcia, J. J. Nogueira, F. Plasser and L. González, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC01684E

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