Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds
Year: 2019
Type: article
Abstract: units dramatically improves the stability of the TTFtt moiety and furthermore enables the isolation of a redox series where the TTF core carries the formal charges of 0, +1, and +2. All of these redox congeners show efficient and clean transmetalation to Ni and Pd resulting in an analogous series of bimetallic complexes capped by 1,2-bis(diphenylphosphino)ethane (dppe) ligands. Furthermore, by using the same transmetalation method, we synthesized analogous palladium complexes capped by 1,1'-bis(diphenylphosphino)ferrocene (dppf) which had been previously reported. All of these species have been thoroughly characterized through a systematic survey of chemical and electronic properties by techniques including cyclic voltammetry (CV), ultraviolet-visible-near infrared spectroscopy (UV-vis-NIR), electron paramagnetic resonance spectroscopy (EPR), nuclear magnetic resonance spectroscopy (NMR) and X-ray diffraction (XRD). These detailed synthetic and spectroscopic studies highlight important differences between the transmetalation strategy presented here and previously reported synthetic methods for the installation of TTFtt. In addition, the utility of this stabilization strategy can be illustrated by the observation of unusual TTF radical-radical packing in the solid state and dimerization in the solution state. Theoretical calculations based on variational 2-electron reduced density matrix methods have been used to investigate these unusual interactions and illustrate fundamentally different levels of covalency and overlap depending on the orientations of the TTF cores. Taken together, this work demonstrates that tin-capped TTFtt units are ideal reagents for the installation of redox-tunable TTFtt ligands enabling the generation of entirely new geometric and electronic structures.
Source: Chemical Science
DOI: 10.1039/c9sc04381k
Institution: University of Chicago
Language: English
Field: Materials Science
Domain: Physical Sciences
Open Access status: diamond
Funders: National Science Foundation, U.S. Department of Energy, University of Chicago, Office of Science, U.S. Army, Materials Research Science and Engineering Center, Harvard University, Division of Materials Research, Division of Chemistry, Basic Energy Sciences, Army Research Office, Argonne National Laboratory
Awards: G102163711, G1055550527, G107546177, Materials Research Science and Engineering Centers, G1286251239, G1313983767, G1505794299, G1664757510, G1673814530, QUANTUM COMPUTING ALGORITHMS AND APPLICATIONS FOR COHERENT AND STRONGLY CORRELATED CHEMICAL SYSTEMS, G2101401529, QUANTUM COMPUTING ALGORITHMS AND APPLICATIONS FOR COHERENT AND STRONGLY CORRELATED CHEMICAL SYSTEMS, G2287611682, G262962599, G2867976162, G2887060908, G2916140176, Two-electron Reduced Density Matrices in Quantum Chemistry and Physics, G3075337988, G340565428, G3535030288, G3589692066, G426311843, G442392651, G459367103, G4644544412, G498139845, G5106849484, G513797252, G5217248309, G5387317844, G5910536577, G657448715, G6599444349, G6848031779, G690747596, G6918803902, G7368700025, G7452299184, G7583137537, G837711380, G969889393, G993149817
OpenAlex ID: W2993809129