Science· 2019Q1· Review
Electronic structure in the transition metal block and its implications for light harvesting
- 369citations
- Q1SCImago
- 2019year
Short summary
First-row transition metal compounds fail at photoinduced electron transfer due to excited-state electronic structure differences, unlike their second/third-row counterparts, despite similar light absorption.
AI-generated from the title and abstract; the full text is not read.
Key points
- First-row transition metal compounds (e.g., Fe, Co) are poor at photoinduced electron transfer.
- Second/third-row analogs (e.g., Ru, Ir) are widely used for light-enabled processes.
- The key difference lies in the excited-state electronic structure, inverted in first-row elements.
- This inversion prevents first-row compounds from engaging in photoinduced electron transfer despite similar light absorption.
AI-generated from the title and abstract; the full text is not read.
Abstract
Transition metal-based chromophores play a central role in a variety of light-enabled chemical processes ranging from artificial solar energy conversion to photoredox catalysis. The most commonly used compounds include elements from the second and third transition series (e.g., ruthenium and iridium), but their Earth-abundant first-row analogs fail to engage in photoinduced electron transfer chemistry despite having virtually identical absorptive properties. This disparate behavior stems from fundamental differences in the nature of 3d versus 4d and 5d orbitals, resulting in an inversion in the compounds' excited-state electronic structure and undermining the ability of compounds with first-row elements to engage in photoinduced electron transfer. This Review will survey the key experimental observations establishing this difference in behavior, discuss the underlying reasons for this phenomenon, and briefly summarize efforts that are currently under way to alter this paradigm and open the door to new opportunities for using Earth-abundant materials for photoinduced electron transfer chemistries.
The authors' abstract, as published at the source. Science, 2019 · DOI ↗
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Field: Electrochemistry
ElectrochemistryChemistry