Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 26, Issue 47, Pages 10801-10810Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202001393
Keywords
density functional calculations; excited state structures; iron spin crossover complexes; optical transient absorption spectroscopy; spin crossover
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Funding
- Severo Ochoa Excellence program from the Instituto IMDEA Nanociencia [SEV-2016-0686]
- Acciones de Dinamizacion Europa Investigacion grant [EIN2019-103399]
- Spanish Ministerio de Ciencia, Innovacion y Universidades [PID2019-111086RA-I00]
- project CALIPSOplus under the EU Framework Programme for Research and Innovation HORIZON 2020 [730872]
- Comunidad de Madrid through TALENTO grant [2017-T1/IND-5432]
- Ayudante de Investigacion grant [PEJ-2019-AI/AMB-13038]
- Spanish MINECO [CTQ2016-80635-P]
- Ramon y Cajal Research program [RYC-2014-16866]
- Comunidad Autonoma de Madrid [PEJD-2017-PRE/IND-4037]
- XALOC-ALBA synchrotron source [2018012561]
- DOE Office of Science [DE-AC02-06CH11357]
- Midscale Instrumentation grant
- New Facility grant
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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 mu s. 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.
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