title: Controlling Near-Infrared Chromophore Electronic Properties through Metal-Ligand Orbital Alignment.
abstract: Transition-metal complexes of radical ligands can exhibit low-energy electronic transitions in the near-infrared (NIR) spectral region. NIR band energy and intensity sensitively depend on the degree of electronic coupling of the chromophore. Using the example of open-shell complexes derived from platinum and a 1,4-terphenyldithiophenol, we present a novel approach toward spectroscopically distinct NIR dyes for which the degree of electronic coupling correlates with the relative orientation of radical ligand and metal orbitals. Ligand/metal orbital alignment is modulated by auxiliary phosphine donors and selectively results in electron localized Class II-III or delocalized Class III structures that display distinct NIR transitions at 6500 and 4000 cm-1.
authors.affiliation: Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Nicole M
authors.initials: NM
authors.lastname: Mews
authors.affiliation: Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Andreas
authors.identifier: 0000-0002-2757-7841
authors.initials: A
authors.lastname: Berkefeld
authors.affiliation: Institut für Chemie, Bioanorganische Chemie, TU Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Gerald
authors.initials: G
authors.lastname: Hörner
authors.affiliation: Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Hartmut
authors.initials: H
authors.lastname: Schubert