title: Control of Complex Formation through Peripheral Substituents in Click-Tripodal Ligands: Structural Diversity in Homo- and Heterodinuclear Cobalt-Azido Complexes.
abstract: The azide anion is widely used as a ligand in coordination chemistry. Despite its ubiquitous presence, controlled synthesis of azido complexes remains a challenging task. Making use of click-derived tripodal ligands, we present here various coordination motifs of the azido ligands, the formation of which appears to be controlled by the peripheral substituents on the tripodal ligands with otherwise identical structure of the coordination moieties. Thus, the flexible benzyl substituents on the tripodal ligand TBTA led to the formation of the first example of an unsupported and solely μ1,1-azido-bridged dicobalt(II) complex. The more rigid phenyl substituents on the TPTA ligand deliver an unsupported and solely μ1,3-azido-bridged dicobalt(II) complex. Bulky diisopropylphenyl substituents on the TDTA ligand deliver a doubly μ1,1-azido-bridged dicobalt(II) complex. Intriguingly, the mononuclear copper(II) complex [Cu(TBTA)N3]+is an excellent synthon for generating mixed dinuclear complexes of the form [(TBTA)Co(μ1,1-N3)Cu(TBTA)]3+or [(TBTA)Cu(μ1,1-N3)Cu(TPTA)]3+, both of which contain a single unsupported μ1,1-N3as a bridge. To the best of our knowledge, these are also the first examples of mixed dinuclear complexes with a μ1,1-N3monoazido bridge. All complexes were crystallographically characterized, and selected examples were probed via magnetometry and high-field EPR spectroscopy to elucidate the electronic structures of these complexes and the nature of magnetic coupling in the various azido-bridged complexes. These results thus prove the power of click-tripodal ligands in generating hitherto unknown chemical structures and properties.
authors.affiliation: Institut für Chemie und Biochemie, Anorganische Chemie , Fabeckstraße 34-36, D-14195, Berlin, Germany.
authors.forename: Michael G
authors.initials: MG
authors.lastname: Sommer
authors.affiliation: Institut für Physikalische Chemie, Universität Stuttgart , Pfaffenwaldring 55, D-70569, Stuttgart, Germany.
authors.forename: Raphael
authors.initials: R
authors.lastname: Marx
authors.affiliation: Institut für Chemie und Biochemie, Anorganische Chemie , Fabeckstraße 34-36, D-14195, Berlin, Germany.
authors.forename: David
authors.initials: D
authors.lastname: Schweinfurth
authors.affiliation: Institut für Physikalische Chemie, Universität Stuttgart , Pfaffenwaldring 55, D-70569, Stuttgart, Germany.
authors.forename: Yvonne
authors.initials: Y
authors.lastname: Rechkemmer
authors.affiliation: Institut für Physikalische Chemie, Universität Stuttgart , Pfaffenwaldring 55, D-70569, Stuttgart, Germany.
authors.forename: Petr
authors.initials: P
authors.lastname: Neugebauer
authors.affiliation: Institut für Chemie und Biochemie, Anorganische Chemie , Fabeckstraße 34-36, D-14195, Berlin, Germany.
authors.forename: Margarethe
authors.initials: M
authors.lastname: van der Meer
authors.affiliation: Institut für Chemie und Biochemie, Anorganische Chemie , Fabeckstraße 34-36, D-14195, Berlin, Germany.
authors.forename: Stephan
authors.initials: S
authors.lastname: Hohloch
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität Göttingen , Tammanstraße 4, D-37077, Göttingen, Germany.
authors.forename: Serhiy
authors.initials: S
authors.lastname: Demeshko
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität Göttingen , Tammanstraße 4, D-37077, Göttingen, Germany.
authors.forename: Franc
authors.identifier: http://orcid.org/0000-0002-8613-7862
authors.initials: F
authors.lastname: Meyer
authors.affiliation: Institut für Physikalische Chemie, Universität Stuttgart , Pfaffenwaldring 55, D-70569, Stuttgart, Germany.
authors.forename: Joris
authors.initials: J
authors.lastname: van Slageren
authors.affiliation: Institut für Chemie und Biochemie, Anorganische Chemie , Fabeckstraße 34-36, D-14195, Berlin, Germany.
authors.forename: Biprajit
authors.identifier: http://orcid.org/0000-0003-4887-7277
authors.initials: B
authors.lastname: Sarkar