Cyano-ambivalence: Spectroscopy and photophysics of [Ru(diimine)(CN-BR3)4]2− complexes

Danh X. Ngo; Sarah A. Del Ciello; Brendon J. McNicholas; Brian C. Sanders; Javier Fajardo; Harry B. Gray; Jay R. Winkler

doi:10.1016/j.poly.2020.114692

Cyano-ambivalence: Spectroscopy and photophysics of [Ru(diimine)(CN-BR₃)₄]²⁻ complexes

Danh X. Ngo
, Sarah A. Del Ciello
, Brendon J. McNicholas
, Brian C. Sanders
, Javier Fajardo
, Harry B. Gray
, Jay R. Winkler

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The UV–visible absorption and luminescence spectra of [Ru(diimine)(CN)₄]²⁻ derivatives have been tuned over wide ranges through variations in solvent, substituents on the diimine ligand, and boronation of the cyanide ligands. Trifluoromethyl substitution at the 4 and 4′ positions of the diimine induces red shifts in metal-to-ligand charge-transfer (MLCT) absorption and luminescence bands. Boronation of the cyanide ligands produces substantial blue shifts in MLCT energies. The combination of diimine trifluoromethylation and cyanide boronation produces MLCT blue shifts that are about 75% as large as those produced by boronation alone.

Original language	English
Article number	114692
Journal	Polyhedron
Volume	188
DOIs	https://doi.org/10.1016/j.poly.2020.114692
State	Published - Sep 15 2020
Externally published	Yes

Funding

The research described in this manuscript is based upon work supported by the National Science Foundation under Grant No. CHE-1763429. Additional support was provided by the Arnold and Mabel Beckman Foundation .

Keywords

Absorption spectra
Boronation
Cyanometalate
Luminescence spectra
Solvatochromism

Access to Document

10.1016/j.poly.2020.114692

Cite this

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title = "Cyano-ambivalence: Spectroscopy and photophysics of [Ru(diimine)(CN-BR3)4]2− complexes",

abstract = "The UV–visible absorption and luminescence spectra of [Ru(diimine)(CN)4]2− derivatives have been tuned over wide ranges through variations in solvent, substituents on the diimine ligand, and boronation of the cyanide ligands. Trifluoromethyl substitution at the 4 and 4′ positions of the diimine induces red shifts in metal-to-ligand charge-transfer (MLCT) absorption and luminescence bands. Boronation of the cyanide ligands produces substantial blue shifts in MLCT energies. The combination of diimine trifluoromethylation and cyanide boronation produces MLCT blue shifts that are about 75\% as large as those produced by boronation alone.",

keywords = "Absorption spectra, Boronation, Cyanometalate, Luminescence spectra, Solvatochromism",

author = "Ngo, \{Danh X.\} and \{Del Ciello\}, \{Sarah A.\} and McNicholas, \{Brendon J.\} and Sanders, \{Brian C.\} and Javier Fajardo and Gray, \{Harry B.\} and Winkler, \{Jay R.\}",

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doi = "10.1016/j.poly.2020.114692",

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T2 - Spectroscopy and photophysics of [Ru(diimine)(CN-BR3)4]2− complexes

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AU - Del Ciello, Sarah A.

AU - McNicholas, Brendon J.

AU - Sanders, Brian C.

AU - Fajardo, Javier

AU - Gray, Harry B.

AU - Winkler, Jay R.

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AB - The UV–visible absorption and luminescence spectra of [Ru(diimine)(CN)4]2− derivatives have been tuned over wide ranges through variations in solvent, substituents on the diimine ligand, and boronation of the cyanide ligands. Trifluoromethyl substitution at the 4 and 4′ positions of the diimine induces red shifts in metal-to-ligand charge-transfer (MLCT) absorption and luminescence bands. Boronation of the cyanide ligands produces substantial blue shifts in MLCT energies. The combination of diimine trifluoromethylation and cyanide boronation produces MLCT blue shifts that are about 75% as large as those produced by boronation alone.

KW - Absorption spectra

KW - Boronation

KW - Cyanometalate

KW - Luminescence spectra

KW - Solvatochromism

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