title: A carboxylate-bridged Ni cluster with a distorted cubane topology: structure, magnetism and density functional studies.
abstract: Using a dicarboxylate ligand appended with (2-pyridyl)ethylamine unit, a new cluster [Ni(L(4))6(DMF)2(CH3OH)2(H2O)6][ClO4]4·2CH3OH·2CH3CO2C2H5 (1) [L(4)(2-): 3-[N-{2-(pyridin-2-yl)ethyl}amino]-bis(propionate)] has been synthesized, through 'coordination-driven self-assembly'. The crystal structure of 1 reveals a centrosymmetric octanuclear carboxylate-bridged nickel(ii) tetracation, with a distorted cubane topology. The four crystallographically independent nickel(ii) centres differ markedly in their coordination environment. Magnetic studies (2-300 K) reveal that in 1 the net magnetic-exchange is antiferromagnetic. Based on geometric parameters associated with two interacting nickel(ii) centres, six magnetic-exchange coupling constants (J values) were considered for magnetic data analysis. Notably, 1 provides the first example of a Ni cluster (i) bridged solely by carboxylates in three bridging modes (monatomic, syn-anti and anti-anti), (ii) exhibiting four ferromagnetic and two antiferromagnetic magnetic-interactions and (iii) demonstrating a good agreement between six J values (obtained from experimental data analysis) and those obtained from DFT calculations, at the B3LYP-level of theory.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016, India. rnm@iitk.ac.in.
authors.forename: Himanshu
authors.initials: H
authors.lastname: Arora
authors.forename: Joan
authors.initials: J
authors.lastname: Cano
authors.forename: Francesc
authors.initials: F
authors.lastname: Lloret
authors.forename: Rabindranath
authors.initials: R
authors.lastname: Mukherjee