title: Targeted self-assembly and quantum Monte Carlo magnetic study of an alternating nickel(II) 1D coordination polymer composed of highly preorganized binuclear tectons.
abstract: A pyrazolate-based binucleating ligand HL with pyridyl groups in the chelate arms has been used to synthesize the dinickel(II) complex [LNi2(N3)(MeOH)2](ClO4)2 (1) and the corresponding 1D polymeric [LNi2(mu-N3)2]n(NO3)n (2) depending on the amount of NaN3 added. X-Ray crystallography shows that structural parameters of the (LNi2(N3)) units are very similar in both compounds. This is ascribed to pi-pi stacking between the pyridyl rings that leads to rigidification of the framework and a fixed cis-orientation of the remaining coordination sites, which are filled by MeOH molecules in or by a mu1,3-bridging azide that connects the subunits in 2. Variable-temperature magnetic measurements reveal strong antiferromagnetic coupling with parameters g = 2.21 and J = -60.7 cm(-1) for compound 1. Magnetic data for the extended chain 2 have been analyzed by Quantum Monte Carlo (QMC) simulations to give g = 2.34, J1 = -55 cm(-1), and J2 = -12 cm(-1). The known J value for finally allows unambiguous assignment of J1 to the intrasubunit coupling within each bimetallic chain constituent. The alternation ratio gamma = J2/J1 signifies a singlet-dimer ground state of the new 1D polymer 2.
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstr. 4, D-37077 Göttingen, Germany.
authors.forename: Feng-Mei
authors.initials: FM
authors.lastname: Nie
authors.forename: Serhiy
authors.initials: S
authors.lastname: Demeshko
authors.forename: Sebastian
authors.initials: S
authors.lastname: Fuchs
authors.forename: Sebastian
authors.initials: S
authors.lastname: Dechert
authors.forename: Thomas
authors.initials: T
authors.lastname: Pruschke
authors.forename: Franc
authors.initials: F
authors.lastname: Meyer