title: Anion-Directed Copper(II) Metallocages, Coordination Chain, and Complex Double Salt: Structures, Magnetic Properties, EPR Spectra, and Density Functional Study.
abstract: A series of Cu(II) metallo-assemblies showing anion-directed structural variations, including five metallocages [(G(n-) )⊂{Cu2 (Hdpma)4 }]((8-n)+) (A(-) )8-n (G(n-) =NO3 (-) , ClO4 (-) , SiF6 (2-) , BF4 (-) , SO4 (2-) ; A(-) =NO3 (-) , ClO4 (-) , BF4 (-) , CH3 SO4 (-) ; Hdpma=bis(3-pyridylmethyl)ammonium cation), a complex double salt, namely, (H3 dpma)4 (CuCl4 )5 Cl2 , and a coordination chain, namely, [Cu2 (dpma)(OAc)4 ], are reported. The influence of the anion can be explained by its coordinating ability, the affinity of which for the Cu(II) center interferes significantly with metallocage formation, and its shape, which offers host-guest recognition ability to engage in weak metal-anion coordination and hydrogen bonding to the organic ligand, which are responsible for metallocage templation. EPR studies of these metallocages in the powder phase at room temperature and 77 K showed a trend of the g values (g|| >2.10>g⊥ >2.00) indicating a dx2-y2 -based ground state with square-pyramidal geometry for the Cu(II) centers. The magnetism of these metallocages can be interpreted as the result of a combination of relatively small magnetic coupling integrals and a substantial contribution of temperature-independent paramagnetism (TIP). The weak magnetic interaction is corroborated by the results of DFT calculations and the EPR spectra. Availability of the low-lying state for spin population was confirmed by a magnetization study, which revealed a magnetic moment approaching 2Nβ, which would explain the presence of the larger TIP term.
authors.affiliation: Department of Applied Chemistry, National Chi Nan University, Nantou, 545, Taiwan. jyunwu@ncnu.edu.tw.
authors.forename: Jing-Yun
authors.initials: JY
authors.lastname: Wu
authors.affiliation: Department of Applied Chemistry, National Chi Nan University, Nantou, 545, Taiwan.
authors.forename: Ming-Shiou
authors.initials: MS
authors.lastname: Zhong
authors.affiliation: Institute of Chemistry, Academia Sinica, Taipei, 115, Taiwan. mhchiang@chem.sinica.edu.tw.
authors.forename: Ming-Hsi
authors.initials: MH
authors.lastname: Chiang
authors.affiliation: Institute of Chemistry, Academia Sinica, Taipei, 115, Taiwan. drdibyendubhattacharya@gmail.com.|Chemistry & Biomimetics Group, CSIR-Central Mechanical Engineering Research Institute, Mahatma Gandhi Avenue, Durgapur, 713 209, India. drdibyendubhattacharya@gmail.com.
authors.forename: Dibyendu
authors.initials: D
authors.lastname: Bhattacharya
authors.affiliation: Department of Applied Chemistry, National Chi Nan University, Nantou, 545, Taiwan.
authors.forename: Yen-Wei
authors.initials: YW
authors.lastname: Lee
authors.affiliation: Department of Applied Chemistry, National Chi Nan University, Nantou, 545, Taiwan.
authors.forename: Long-Li
authors.initials: LL
authors.lastname: Lai
keywords: N ligands; cage compounds; copper; host-guest systems; self-assembly