Synthesis, spectroscopic and electrochemical properties, and electronic structures of octahedral hexatechnetium(III) clusters [Tc6Q 8(CN)6]4? (Q = S, Se)

Takashi Yoshimura, Takuya Ikai, Tsutomu Takayama, Tsutomu Sekine, Yasushi Kino, Atsushi Shinohara

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)

Abstract

Chalcogenide-capped molecular octahedral hexatechnetium(III) clusters [Tc6Q8(CN)6]4? {Q = S ([1] 4?), Se ([2]4?)} were prepared by the substitution of axial ligands with cyanide. The structures of the new complexes were determined by single-crystal X-ray analysis. The IR spectra of [1]4? and [2]4? showed a C - N stretching band at 2114 and 2105 cm ?1, respectively. In cyclic voltammetry, [1]4? and [2]4? in CH3CN showed reversible one-electron-oxidation waves assignable to the Tc6(24e/23e) process at +0.99 and +0.74 V, respectively. Density functional theory (DFT) calculations on the hexatechnetium complexes showed that the highest occupied molecular orbital (HOMO) was primarily localized on a Tc6Q8 core and the lowest unoccupied molecular orbital (LUMO) was completely localized on the metal orbitals. The energy level of HOMO and the redox potential of the M 6(24e/23e) process (M = Tc, Re) were found to have a good linear relationship. Time-dependent DFT calculations showed that the substantially allowed transitions with the lowest energy were Tc6Q8 core-centered transitions. The electronic structures and electronic transition features of the hexatechnetium complexes were similar to those of the hexarhenium analogues [Re6Q8(CN)6]4? (Q = S, Se); however, the energy gap between the HOMO and LUMO was smaller in the hexatechnetium complexes.

Original languageEnglish
Pages (from-to)5876-5882
Number of pages7
JournalInorganic Chemistry
Volume49
Issue number13
DOIs
Publication statusPublished - 2010 Jul 5

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Synthesis, spectroscopic and electrochemical properties, and electronic structures of octahedral hexatechnetium(III) clusters [Tc<sub>6</sub>Q <sub>8</sub>(CN)<sub>6</sub>]<sup>4?</sup> (Q = S, Se)'. Together they form a unique fingerprint.

Cite this