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- W4297347013 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." @default.
- W4297347013 created "2022-09-28" @default.
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- W4297347013 date "2022-09-27" @default.
- W4297347013 modified "2023-10-14" @default.
- W4297347013 title "Borylation in the Second Coordination Sphere of Fe<sup>II</sup> Cyanido Complexes and Its Impact on Their Electronic Structures and Excited-State Dynamics" @default.
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- W4297347013 doi "https://doi.org/10.1021/acs.inorgchem.2c01667" @default.
- W4297347013 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/36167335" @default.
- W4297347013 hasPublicationYear "2022" @default.
- W4297347013 type Work @default.