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Borylation in the Second Coordination Sphere of FeIICyanido Complexes and Its Impact on Their Electronic Structures and Excited-State Dynamics

Schmid, Lucius ; Chábera, Pavel LU ; Rüter, Isabelle ; Prescimone, Alessandro ; Meyer, Franc ; Yartsev, Arkady LU orcid ; Persson, Petter LU and Wenger, Oliver S. (2022) In Inorganic Chemistry 61(40). p.15853-15863
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)3resulted in several particularly interesting new compounds lately. Here, we investigate the effects of borylation on the properties of two FeIIcyanido 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... (More)

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)3resulted in several particularly interesting new compounds lately. Here, we investigate the effects of borylation on the properties of two FeIIcyanido 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)3attachment at the cyanido N lone pair.

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author
; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
61
issue
40
pages
11 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:36167335
  • scopus:85139238460
ISSN
0020-1669
DOI
10.1021/acs.inorgchem.2c01667
language
English
LU publication?
yes
id
e40b4ec7-37ed-4726-b295-e1bde9438117
date added to LUP
2022-12-14 12:46:20
date last changed
2025-03-17 17:46:42
@article{e40b4ec7-37ed-4726-b295-e1bde9438117,
  abstract     = {{<p>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(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>resulted in several particularly interesting new compounds lately. Here, we investigate the effects of borylation on the properties of two Fe<sup>II</sup>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 Fe<sup>II</sup>-based t<sub>2g</sub>-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(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>attachment at the cyanido N lone pair.</p>}},
  author       = {{Schmid, Lucius and Chábera, Pavel and Rüter, Isabelle and Prescimone, Alessandro and Meyer, Franc and Yartsev, Arkady and Persson, Petter and Wenger, Oliver S.}},
  issn         = {{0020-1669}},
  language     = {{eng}},
  month        = {{10}},
  number       = {{40}},
  pages        = {{15853--15863}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Inorganic Chemistry}},
  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}},
  url          = {{http://dx.doi.org/10.1021/acs.inorgchem.2c01667}},
  doi          = {{10.1021/acs.inorgchem.2c01667}},
  volume       = {{61}},
  year         = {{2022}},
}