Effects of cis/trans‐Configuration and Ligand Substitution of the Cyanidometal Bridge on Metal to Metal Charge Transfer Properties in Mixed Valence Complexes

Abstract

To investigate the effects of cis/trans-configuration of the cyanidometal bridge and the electron donating ability of the auxiliary ligand on the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged mixed valence compounds, two groups of trinuclear cyanidometal-bridged compounds cis/trans-(cis/trans-2[PF 6 ] 3 ) were synthesized and fully characterized. The exper-imental results indicate that for these one-and two-electron oxidation mixed valence compounds, the trans-configuration compounds are more beneficial for MMCT than the cisconfiguration compounds, and increasing the electron donating ability of the auxiliary ligand on the cyanidometal bridge is also conductive to MMCT. Moreover, compounds cis/trans-1[PF 6 ] n (n = 3, 4) and cis/trans-2[PF 6 ] 3 belong to localized compounds by analyzing the experimental characterization results, supported by the TDDFT calculations.

Investigation of the electron transfer properties between metal centers in binuclear and trinuclear cyanido-bridged mixed valence complexes with cis/trans-configuration

“…33,34 Most recently, our group has reported two groups of trinuclear cyanidometal-bridged complexes with cis/trans configuration for the investigation of the influence of the cis/trans-configuration of the cyanidometal bridge and its ancillary ligand on the electron transfer properties between metal centers. 35 To date, however, the influence of the cis/trans-configuration of the central cyanidometal bridge on electron transfer properties between metal centers has been relatively poorly studied. In addition, the influence of the presence of the other terminal metal fragment on the electron transfer properties between adjacent metal centers has also been less studied in polynuclear cyanido-bridged mixed-valence complexes.…”