Tracking the Light-Induced Excited-State Dynamics and Structural Configurations of an Extraordinarily Long-Lived Metastable State at Room Temperature

Iglesias S, Gamonal A, Abudulimu A, Picon A, Carrasco E, Ecija D, Liu C, Luer L, Zhang X, Costa JS, Moonshiram D (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Chemistry - A European Journal Wiley

DOI: 10.1002/chem.202001393

Abstract

Time-resolved X-ray (Tr-XAS) and optical transient absorption (OTA) spectroscopy on the pico-microsecond timescale coupled with density functional theory calculations are applied to study the light-induced spin crossover processes of a Fe-based macrocyclic complex in solution. Tr-XAS analysis after light illumination shows the formation of a seven-coordinated high-spin quintet metastable state, which relaxes to a six-coordinated high-spin configuration before decaying to the ground state. Kinetic analysis of the macrocyclic complex reveals an unprecedented long-lived decay lifetime of approximately 42.6 μs. Comparative studies with a non-macrocyclic counterpart illustrate a significantly shortened approximately 568-fold decay lifetime of about 75 ns, and highlight the importance of the ligand arrangement in stabilizing the reactivity of the excited state. Lastly, OTA analysis shows the seven-coordinated high-spin state to be formed within approximately 6.2 ps. These findings provide a complete understanding of the spin crossover reaction and relaxation pathways of the macrocyclic complex, and reveal the importance of a flexible coordination environment for their rational design.

Additional Organisation(s)

Institute Materials for Electronics and Energy Technology (i-MEET)

Involved external institutions

IMDEA-Nanociencia ES Spain (ES) Argonne National Laboratory US United States (USA) (US) Universidad Autónoma de Madrid (UAM) ES Spain (ES)

How to cite

APA:

Iglesias, S., Gamonal, A., Abudulimu, A., Picon, A., Carrasco, E., Ecija, D.,... Moonshiram, D. (2020). Tracking the Light-Induced Excited-State Dynamics and Structural Configurations of an Extraordinarily Long-Lived Metastable State at Room Temperature. Chemistry - A European Journal. https://dx.doi.org/10.1002/chem.202001393

MLA:

Iglesias, Sirma, et al. "Tracking the Light-Induced Excited-State Dynamics and Structural Configurations of an Extraordinarily Long-Lived Metastable State at Room Temperature." Chemistry - A European Journal (2020).

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