Anion-Directed Copper(II) Metallocages, Coordination Chain, and Complex Double Salt: Structures, Magnetic Properties, EPR Spectra, and Density Functional Study

A series of CuII metallo‐assemblies showing anion‐directed structural variations, including five metallocages [(Gn−)⊂{Cu2(Hdpma)4}](8−n)+(A−)8−n (Gn−=NO3−, ClO4−, SiF62−, BF4−, SO42−; A−=NO3−, ClO4−, BF4−, CH3SO4−; Hdpma=bis(3‐pyridylmethyl)ammonium cation), a complex double salt, namely, (H3dpma)4(CuCl4)5Cl2, 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 CuII 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 CuII 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. Supramolecular metallo‐assemblies: Five anion‐templated metallocages, a complex double salt, and a coordination chain were obtained by self‐assembly from dpma/CuX2/HX or dpma/CuSO4/H2SO4 systems (see scheme; dpma=bis(3‐pyridylmethyl)amine). Formation of the metallocages is due to the shape of the anion and coordination and hydrogen‐bonding interactions of the anionic guest with the cationic {Cu2(μ‐Hdpma)4} host.