Probing the Intrinsic Electronic Structure of the Bis(dithiolene) Anions [M(mnt)2]2- and [M(mnt)2]1- (M=Ni, Pd, Pt; mnt=1,2-S2C2(CN)2) in the Gas Phase By Photoelectron Spectroscopy

Journal Article · Sat Mar 11 04:00:00 EST 2006 · Journal of the American Chemical Society, 128(13):4282-4291

DOI:https://doi.org/10.1021/ja056342s· OSTI ID:882972

Waters, Tom; Woo, Hin-koon; Wang, Xue B; Wang, Lai S

A detailed understanding of the electronic structure of transition metal bis(dithiolene) complexes is important because of their interesting redox, magnetic, optical, and conducting properties and their relevance to enzymes containing molybdenum and tungsten bis(dithiolene) centers. The electronic structures of the bis(dithiolene) anions [M(mnt)2] n- (M ) Ni, Pd, Pt; mnt ) 1,2-S2C2(CN)2; n) 0-2) were examined by a combination of photodetachment photoelectron spectroscopy (PES) and density functional theory calculations. The combined experimental and theoretical data provide insight into the molecular orbital energy levels of [M(mnt)2]2- and the ground and excited states of [M(mnt)2]1- and [M(mnt)2]. Detachment features from ligand-based orbitals of [M(mnt)2]2- occur at similar energies for each species, independent of the metal center, while those arising from metal-based orbitals occur at higher energies for the heavier congeners. Electronic excitation energies inferred for [M(mnt)2]1- from the PES experiments agree well with those obtained in optical absorption experiments in solution, with the PES experiments providing additional insight into the changes in energy of these transitions as a function of metal. The singly charged anions [M(mnt)2]1- were also prepared and studied independently. Electron detachment from the ground states of these doublet anions accessed the lowest singlet and triplet states of neutral [M(mnt)2], thereby providing a direct experimental measure of their singlet-triplet splitting.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 882972
• Report Number(s): PNNL-SA-49810; 3223; 8592; 25392; KP1704020
• Journal Information: Journal of the American Chemical Society, 128(13):4282-4291, Journal Name: Journal of the American Chemical Society, 128(13):4282-4291
• Country of Publication: United States
• Language: English

Related Subjects

Environmental Molecular Sciences Laboratory