title: Dual charge-transfer in rhenium(I) thioether substituted hexaazanaphthalene complexes.
abstract: The ligand 2,3,8,9,14,15-hexa(octyl-thioether)-5,6,11,12,17,18-hexaazatrinaphthalene (HATN-(SOct)6) and its mono-, bi-, and trinuclear Re(CO)3Cl complexes are reported. These are characterized by (1)H NMR spectroscopy and electrochemistry, and show broad, intense absorption across the visible wavelength region. Using time-dependent density functional theory (TD-DFT) calculations and resonance Raman spectroscopy these absorption bands are shown to be π → π*, MLCT, ILCT(sulfur → HATN), or mixed MLCT/ILCT in nature. Time-resolved infrared spectroscopy is used to probe structural changes and dynamics on short time scales and supports the assignment of a mixed MLCT/ILCT state in which both sulfur groups and one metal center act as electron donors to the HATN core.
authors.affiliation: Department of Chemistry and MacDiarmid Institute, University of Otago , Union Place, 9016 Dunedin, New Zealand.
authors.forename: Holly
authors.initials: H
authors.lastname: van der Salm
authors.forename: Michael G
authors.initials: MG
authors.lastname: Fraser
authors.forename: Raphael
authors.initials: R
authors.lastname: Horvath
authors.forename: Jack O
authors.initials: JO
authors.lastname: Turner
authors.forename: Gregory M
authors.initials: GM
authors.lastname: Greetham
authors.forename: Ian P
authors.initials: IP
authors.lastname: Clark
authors.forename: Michael
authors.initials: M
authors.lastname: Towrie
authors.forename: Nigel T
authors.initials: NT
authors.lastname: Lucas
authors.forename: Michael W
authors.initials: MW
authors.lastname: George
authors.forename: Keith C
authors.initials: KC
authors.lastname: Gordon