Solvothermal Synthesis, Structure, Fluorescence and Magnetism Properties of a Novel 3D Metal-Organic Framework Based on Tetranuclear Copper Secondary Building Units

Abstract

A novel 3D metal-organic framework based on tetranuclear copper Secondary Building Units, [Cu2(μ3-OH)(4-oip)(DMF)]·DMF·2H2O (JUC-76) (4-oip = 4-hydroxyisophthalic, DMF =N,N-dimethylformamide, and JUC = Jilin University China), has been synthesized under solvothermal conditions. It crystallizes in monoclinic symmetry with space groupP21/n. JUC-76 possesses a three-dimensional network with one-dimensional rhombic channels of approximately 13.6 × 8.5 Å2along the [100] direction. The resulting structure of JUC-76 is a distorted rutile topology with one 3-connected organic node and one 6-connected inorganic node. And its Schläfli symbol is (4·62)2(42·610·83). In addition, JUC-76 exhibits fluorescence emission at 446 nm, and a dominant anti-ferromagnetic interaction between the Cu (II) ions.

Coordination Properties of Hydroxyisophthalic Acids: Topological Correlations, Synthesis, Structural Analysis, and Properties of New Complexes

“…[2] A complex of tetranuclear copper(II) secondary building units with 4-hydroxyisophthalate of the JUC-76 family exhibits fluorescence emission and a dominant anti-ferromagnetic interaction between the Cu 2 + ions. [3] Exceptional hydrogen storage capacity was observed for the frameworks M 2 (4,6-oxyisophthalate) (M=Co II , Cu II , Fe II , Ni II , Mg II , Mn II , Zn II ) together with separation of xylene isomers and olefin/paraffin mixtures. [4] Independently to the porosity the compounds with 5-hydroxyisopthalic acid (H 2 -5-hip) and 4hydroxyisophthalic acid (H 2 -4-hip) capable of emitting light under UV irradiation.…”

“…[6] The presence of paramagnetic centers Ce IV , Co II , Cu II , Mn II , Nd III , or Pr III closely distanced to each other within polynuclear rod-like secondary building units leads to antiferromagnetic interactions. [3,7] Ferromagnetic behavior was found for [Nd(5-hip)(H-5-hip)(H 2 O) 2 ] • 2H 2 O. [8] The addition of several hydroxy groups promotes greater diversity of possible coordination modes and properties as compared to isophthalic acid.…”