title: Syntheses, structures, and magnetic properties of three new cyano-bridged complexes based on the [Mn(CN)₆](³⁻) building block.
abstract: With three pentadentate macrocyclic ligands, three new [Mn(CN)6](3-) based complexes, [Mn(L(N3O2))(H2O)]2[Mn(CN)6](ClO4)·3H2O (1), {[Mn(L(N5))]3[Mn(CN)6]2}n (2) and {[Mn(L(N5Me))]3[Mn(CN)6]2}n·10nH2O (3) (L(N3O2) = 2,13-dimethyl-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene, L(N5) = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene, L(N5Me) = 2,6-bis[1-(2-(N-methylamino)ethylimino)ethyl]-pyridine), have been synthesized and characterized structurally and magnetically. The structure of 1 was found to be a linear Mn2(II)Mn(III) trinuclear cluster with two Mn(II) capping groups and one Mn(III) ion connected via two trans-cyano groups. In contrast, compounds 2 and a3 re cyano-bridged 2D networks. Magnetic investigation revealed antiferromagnetic coupling between the Mn(III) and Mn(II) ions via the bridging cyanide groups. Complex 1 showed paramagnetic behavior down to 2.0 K with no sign of SMM behavior. The magnetic coupling constant of J = -1.63 cm(-1) with the Hamiltonian H = -2J(S(Mn(III))·SMn(II)1 + SMn(III)·S(Mn(II)2)) was obtained from the fitting of the magnetic susceptibility. For 2 and 3, ferrimagnetic ordering was observed with magnetic phase transition temperatures (Tc) being 7.5 K and 7.0 K, respectively. These compounds are rare examples of a small number of [Mn(CN)6](3-) based magnetic materials.
authors.affiliation: State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China. wangxy66@nju.edu.cn.
authors.forename: Shao-Liang
authors.initials: SL
authors.lastname: Zhang
authors.forename: Xin-Hua
authors.initials: XH
authors.lastname: Zhao
authors.forename: Xin-Yi
authors.initials: XY
authors.lastname: Wang