Borylation in the Second Coordination Sphere of Fe II Cyanido Complexes and Its Impact on Their Electronic Structures and Excited-State Dynamics
2022 | journal article. A publication with affiliation to the University of Göttingen.
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Borylation in the Second Coordination Sphere of Fe II Cyanido Complexes and Its Impact on Their Electronic Structures and Excited-State Dynamics
Schmid, L.; Chábera, P.; Rüter, I.; Prescimone, A.; Meyer, F. ; Yartsev, A. & Persson, P. et al. (2022)
Inorganic Chemistry, art. acs.inorgchem.2c01667. DOI: https://doi.org/10.1021/acs.inorgchem.2c01667
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Details
- Authors
- Schmid, Lucius; Chábera, Pavel; Rüter, Isabelle; Prescimone, Alessandro; Meyer, Franc ; Yartsev, Arkady; Persson, Petter; Wenger, Oliver S.
- Abstract
- Second coordination sphere interactions of cyanido complexes with hydrogen-bonding solvents and Lewis acids are known to influence their electronic structures, whereby the non-labile attachment of B(C6F5)3 resulted in several particularly interesting new compounds lately. Here, we investigate the effects of borylation on the properties of two FeII cyanido complexes in a systematic manner by comparing five different compounds and using a range of experimental techniques. Electrochemical measurements indicate that borylation entails a stabilization of the FeII-based t2g-like orbitals by up to 1.65 eV, and this finding was confirmed by Mössbauer spectroscopy. This change in the electronic structure has a profound impact on the UV–vis absorption properties of the borylated complexes compared to the non-borylated ones, shifting their metal-to-ligand charge transfer (MLCT) absorption bands over a wide range. Ultrafast UV–vis transient absorption spectroscopy provides insight into how borylation affects the excited-state dynamics. The lowest metal-centered (MC) excited states become shorter-lived in the borylated complexes compared to their cyanido analogues by a factor of ∼10, possibly due to changes in outer-sphere reorganization energies associated with their decay to the electronic ground state as a result of B(C6F5)3 attachment at the cyanido N lone pair.
- Issue Date
- 2022
- Journal
- Inorganic Chemistry
- Organization
- Institut für Anorganische Chemie
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Language
- English