title: Thiophene-Fused Nickel Dithiolenes: A Synthetic Scaffold for Highly Delocalized π-Electron Systems.
abstract: A series of thiophene-fused nickel dithiolene complexes have been prepared via synthetic methods which allow the addition of peripheral aryl groups to the fused thiophene of the dithiolene ligand, thus providing access to a range of structural and electronic modifications to the dithiolene core. X-ray structural studies of the anionic complexes show that the peripheral aryl rings lie in near-perfect coplanarity to the dithiolene core and can form π-stacked columns with N-methylpyridinium cations. Density functional theory calculations show significant delocalization of the frontier orbital electron density into the peripheral aryl rings. The complexes exhibit tunable, intense near-IR (NIR) absorption in the range of 1076-1160 nm with molar absorptivity as high as 25100 M-1cm-1in solution. The electronic tunability as well as the desirable solid-state packing arrangements of these systems suggests significant potential as NIR-absorbing materials for optoelectronic applications.
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Department 2735, P.O. Box 6050, Fargo, North Dakota 58108, United States.
authors.forename: Chad M
authors.initials: CM
authors.lastname: Amb
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Department 2735, P.O. Box 6050, Fargo, North Dakota 58108, United States.
authors.forename: Christopher L
authors.initials: CL
authors.lastname: Heth
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Department 2735, P.O. Box 6050, Fargo, North Dakota 58108, United States.
authors.forename: Sean J
authors.initials: SJ
authors.lastname: Evenson
authors.affiliation: Center for Nanoscale Science and Engineering, North Dakota State University , Fargo, North Dakota 58102, United States.
authors.forename: Konstantin I
authors.initials: KI
authors.lastname: Pokhodnya
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Department 2735, P.O. Box 6050, Fargo, North Dakota 58108, United States.
authors.forename: Seth C
authors.initials: SC
authors.lastname: Rasmussen