title: Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni(II)2(L)(μ(1,1)-N3)][ClO4] (L = Macrocyclic N6S2 Ligand).
abstract: The dinuclear Ni(II) complex [Ni2(L(2))][ClO4]2 (3) supported by the 28-membered hexaaza-dithiophenolate macrocycle (L(2))(2-) binds the N3(-) ion specifically end-on yielding [Ni2(L(2))(μ(1,1)-N3)][ClO4] (7) or [Ni2(L(2))(μ(1,1)-N3)][BPh4] (8), while the previously reported complex [Ni2L(1)(μ(1,3)-N3)][ClO4] (2) of the 24-membered macrocycle (L(1))(2-) coordinates it in the end-to-end fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its preorganized, channel-like binding pocket, which accommodates the azide anion via repulsive CH···π interactions in the end-on mode. In contrast to [Ni2L(1)(μ(1,3)-N3)][ClO4] (2), which features a S = 0 ground state, [Ni2(L(2))(μ(1,1)-N3)][BPh4] (8) has a S = 2 ground state that is attained by competing antiferromagnetic and ferromagnetic exchange interactions via the thiolato and azido bridges with a value for the magnetic exchange coupling constant J of 13 cm(-1) (H = -2JS1S2). These results are further substantiated by density functional theory calculations. The stability of the azido-bridged complex determined by isothermal titration calorimetry in MeCN/MeOH 1/1 v/v (log K11 = 4.88(4) at I = 0.1 M) lies in between those of the fluorido- (log K11 = 6.84(7)) and chlorido-bridged complexes (log K11 = 3.52(5)). These values were found to compare favorably well with the equilibrium constants derived at lower ionic strength (I = 0.01 M) by absorption spectrophotometry (log K11 = 5.20(1), 7.77(9), and 4.13(3) for N3(-), F(-), and Cl(-) respectively).
authors.affiliation: Institut für Anorganische Chemie, Universität Leipzig , Johannisallee 29, 04103 Leipzig, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Jeremies
authors.affiliation: Institut für Anorganische Chemie, Universität Leipzig , Johannisallee 29, 04103 Leipzig, Germany.
authors.forename: Sina
authors.initials: S
authors.lastname: Gruschinski
authors.affiliation: Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR 6302, CNRS, Université de Bourgogne-Franche Comté , 9 avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France.
authors.forename: Michel
authors.initials: M
authors.lastname: Meyer
authors.affiliation: Research Institute for Physical Chemical Problems of Belarusian State University, Leningradskaya 14, 220030 Minsk, Belarus.
authors.forename: Vitaly
authors.initials: V
authors.lastname: Matulis
authors.affiliation: Belarusian State University , 4 Nezavisimisti Avenue, 220050 Minsk, Belarus.
authors.forename: Oleg A
authors.initials: OA
authors.lastname: Ivashkevich
authors.affiliation: Institut für Anorganische Chemie, Universität Leipzig , Johannisallee 29, 04103 Leipzig, Germany.
authors.forename: Karolin
authors.initials: K
authors.lastname: Kobalz
authors.affiliation: Institut für Anorganische Chemie, Universität Leipzig , Johannisallee 29, 04103 Leipzig, Germany.
authors.forename: Berthold
authors.initials: B
authors.lastname: Kersting