Tuning of Valence States, Bonding Types, Hierarchical Structures, and Physical Properties in Copper/Halide/Isonicotinate System

Abstract

Seven cupric halide coordination polymers, namely [Cu5(OH)3Br3(ina)4] (1), [Cu5(OH)3Cl3(ina)4] (2), [Cu2(OH)Cl(ina)2] (3), [Cu3(OH)2Cl2(ina)2]·2H2O (4), [Cu3(OH)2Br2(ina)2]·2H2O (5), [Cu2Cl2(ina)2(H2O)2] (6), [Cu2Cl(ina)2(gca)(H2O)] (7), cupric complex templated cuprous halide [Cu(II)(Me-ina)2(H2O)][Cu(I)5Br7] (8), and organic templated cuprous halide Me2-ina[Cu2Br3] (9) (Hina = isonicotinic acid), were prepared from the starting materials of cupric halide and Hina via fine-tuning solvothermal reactions. According to valence states of copper, 1-7 are copper(II) complexes, 8 is a mixed-valent Cu(I,II) complex, while 9 is a Cu(I) compound. According to bonding types of halides, nine complexes can be classified as three types: complexes 1-3 include only normal X-Cu bond (X = halide); complexes 4-7 include normal X-Cu bond and X···Cu weak bond; complexes 8 and 9 include normal X-Cu bond and X···H-C halogen hydrogen bonds. Complexes 1 and 2 are isomorphic three-dimensional (3D) pcu topological metal organic frameworks (MOFs) with butterfly-like Cu4(μ3-OH)2X2 and steplike Cu6(μ3-OH)4 cores as nodes, showing strong ferromagnetic couplings. Complex 3 also is a pcu topological MOF with only butterfly-like Cu4(μ3-OH)2Cl2 clusters as nodes, presenting spin canting antiferromagnetic behavior. Isostructural 4 and 5 are Cu3(OH)2 clusters based two-dimensional (2D) (4,4) layers, which are extended into 3D eight-connected networks via weak Cu···X bonds, showing ferromagnetic coupling. Antiferromagnetic 6 is a simple one-dimensional coordination polymer, which is extended via weak Cu···Cl bonds into 3D (3,4)-connected networks. Paramagnetic 7 is a ladderlike polymer, which is extended into 2D (3,4)-connected layer via weak Cu···Cl bonds. The syntheses of polymeric cupric complexes 1-7 mainly result from differences in reactant ratio and pH value. Utilization of reducing methanol generated novel cubane-containing [Cu5Br7](2-) chain templated by paddlewheel-like [Cu(II)(Me-ina)2](2+) 8 and face-shared dimer-containing [Cu2Br3](-) chain templated by N-methylated and O-esterificated Me2-ina 9. Complex 9 exhibits a strong red emission and a weaker green emission upon excitation.

Computational Prediction of Metal Organic Frameworks Suitable for Molecular Infiltration as a Route to Development of Conductive Materials

“…Spin polarization was included to consider the magnetic ground state of MOFs, and antiferromagnetic ordering was considered for Cu paddlewheels as reported in literature. 22,[34][35][36] The Brillouin zone was sampled at the Γ-point only; this is sufficient considering the size of the studied systems.…”

Ionothermal synthesis and crystal structure of a new organic–inorganic hybrid compound:catena-poly[bis(1-ethyl-3-methylimidazolium) [hepta-μ-bromido-pentacuprate(I)]]

“…For example, in the preparation of Cu complexes with ethylenediamine, Hammond et al (2001) started with CuBr or a CuBr/CuBr 2 mixture, and in both cases mixed-valence complexes were obtained. Liu et al (2014) also prepared mixed-valence Cu I,II or pure Cu I complexes using CuBr 2 as a reactant in the presence of isonicotinic acid. All the mentioned compounds belong to the group of bromidocuprates(I).…”

“…Among hybrid compounds reported so far, copper(I) halides with different organic templates have been widely investigated due to their rich photoluminescent properties and intriguing topologies (Graham et al, 2000;Wang et al, 2002;Peng et al, 2010;Xin et al, 2013;Liu et al, 2014). Copper(I) tends to form a variety of coordination compounds with halides, ranging from zero-dimensional complexes to three-dimensional frameworks (Subramanian & Hoffmann, 1992;Peng et al, 2010;Gao et al, 2010;Liu et al, 2014). The introduction of organic molecules in the synthesis of polynuclear copper(I) halides is the most extensively and effectively employed strategy to modulate copper(I) halide structures (Xin et al, 2013).…”

Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance

“…[13-14, 19, 51-52] Zhang, Fu, and co-workers.d iscovered as eries of iodocuprates(I) and iodoargentates,s omeo fw hich exhibit photocatalytic properties and interesting photochromic behavior. [18,[53][54][55][56][57] The organic templates have an important role in structural construction,e lectronic band design as well as photoelectric property regulation. Therefore, the reasonable choice of organic species wasp rovedt ob ean effective route for the development multi-functional metal halide-based hybrids.…”