Interligand communication in a metal mediated LL'CT system - a case study

DOI

10.1039/d1ra04716g

Authors

Sara A. Dille, Department of Chemistry and Chemical Biology, Indiana University - Purdue University Indianapolis Indianapolis IN 46202 USA basup@iupui.edu.
Kyle J. Colston, Department of Chemistry and Chemical Biology, Indiana University - Purdue University Indianapolis Indianapolis IN 46202 USA basup@iupui.edu.
Stephen C. Ratvasky, Department of Chemistry and Biochemistry, Duquesne University Pittsburgh PA 15282 USA.
Jingzhi Pu, Department of Chemistry and Chemical Biology, Indiana University - Purdue University Indianapolis Indianapolis IN 46202 USA basup@iupui.edu.
Partha Basu, Department of Chemistry and Chemical Biology, Indiana University - Purdue University Indianapolis Indianapolis IN 46202 USA basup@iupui.edu.

Document Type

Journal Article

Publication Date

1-1-2021

Publication Title

RSC advances

Volume

11

Issue

39

First Page

24381

Last Page

24386

Abstract

A series of oxo-Mo(iv) complexes, [MoO(Dt)(Dt)] (where Dt = benzene-1,2-dithiol (bdt), toluene-3,4-dithiol (tdt), quinoxaline-2,3-dithiol (qdt), or 3,6-dichloro-benzene-1,2-dithiol (bdtCl); Dt = ,'-dimethylpiperazine-2,3-dithione (MeDt) or ,'-diisopropylpiperazine-2,3-dithione ( PrDt)), possessing a fully oxidized and a fully reduced dithiolene ligand have been synthesized and characterized. The assigned oxidation states of coordinated dithiolene ligands are supported with spectral and crystallographic data. The molecular structure of [MoO(tdt)( PrDt)] () demonstrates a large ligand fold angle of 62.6° along the S⋯S vector of the Dt ligand. The electronic structure of this system is probed by density functional theory (DFT) calculations. The HOMO is largely localized on the Dt ligand while virtual orbitals are mostly Mo and Dt in character. Modeling the electronic spectrum of with time dependent (TD) DFT calculations attributes the intense low energy transition at ∼18 000 cm to a ligand-to-ligand charge transfer (LL'CT). The electron density difference map (EDDM) for the low energy transition depicts the electron rich Dt ligand donating charge density to the redox-active orbitals of the electron deficient Dt ligand. Electronic communication between dithiolene ligands is facilitated by a Mo-monooxo center and distortion about its primary coordination sphere.

Open Access

OA

Preprint

Additional Link

Repository Citation

Dille, S. A., Colston, K. J., Ratvasky, S. C., Pu, J., & Basu, P. (2021). Interligand communication in a metal mediated LL'CT system - a case study. RSC advances, 11 (39), 24381-24386. https://doi.org/10.1039/d1ra04716g