Photodimerization behaviour of 1D-3D Zn(II) coordination polymers with tetrazolyl styrylpyridine.

The [2 + 2] photodimerization of tetrazolyl styrylpyridine leads to single-crystal-to-single-crystal transformations of four Zn(II) coordination polymers with 1D-3D structures, exhibiting controllable reaction extent, luminescence decrease or blue shift, and a two-step reaction process with a phase transition point.

Pyrolytic cavitation, selective adsorption and molecular recognition of a porous Eu(III) MOF.

A channel-equipped metal-organic framework (1-pyr), resulting from the pyrolysis of [(CH3)2NH2]@[Eu2L3(HCOO)] (1) (L(2-) = isophthalate), showed the preferable absorption of CO2 and the Eu(III)-based emission quenched by aromatics.

Mixed-valence Cu(II)Cu(I)15I17 cluster builds up a 3D metal-organic framework with paramagnetic and thermochromic characteristics.

Four cubane-like Cu4I4 units are assembled around an iodine atom to form the giant, mixed-valent Cu(II)Cu(I)15I17 cluster. The Cu(II)Cu(I)15I17 cluster and a bipyrazole linker form a 3D open framework with paramagnetic and thermochromic properties. This paper also touches on the resemblance of this cluster to the self-similar object of a Sierpinski tetrahedron.

Novel thermochromism relating to supramolecular cuprophilic interaction: design, synthesis, and luminescence of copper(I) pyrazolate trimer and polymer.

Solvothermal reactions of 4-(pyrid-4'-yl)-3,5-dimethylpyrazole (HPpz) with CuBr in two mixed solvents, NH3.H2O/EtOH and NH3.H2O/MeCN, afforded respectively a copper(I) trimer, [Cu(Ppz)]3(1), and a polymer, {[Cu(Ppz)]3[CuCN] 3} (2), both containing the [Cu(Ppz)]3 entity as a building block. The products were found to be photoluminescent and, more interestingly, when cooled from room temperature to 10 K, they showed a blue shift followed by a red shift (hereafter shortened to a red-after-blue shift) of emission.

From encapsulation to polypseudorotaxane: unusual anion networks driven by predesigned metal bis(terpyridine) complex cations.

Solvothermal reactions of CuSCN, metal (Mn2+, Fe2+, Co2+, Ni2+, Cu2+) sulfate, and terpyridine (2,2':6',2' '-terpyridine or 4'-p-tolyl-2,2':6',2' '-terpyridine) in the presence of triphenylphosphine yielded a series of hybrid coordination compounds, in which in situ formed metal bis(terpyridine) complex cations are encapsulated by a 3D anionic network or entangled by 2D heartlike networks, forming encapsulation or polypseudorotaxane supramolecules. The complex cations play a role as template to direct the fabrication of the structures.

Design and solvothermal synthesis of luminescent copper(I)-pyrazolate coordination oligomer and polymer frameworks.

Two luminescent coordination compounds, [Cu(Pz)]3 (1) and [Cu2(Bpz)]n (2), were isolated from solvothermal reactions of Cu(NO3)2 with 3,5-dimethylpyrazole (HPz) and 3,3',5,5'-tetra-methyl-4,4'-bipyrazole (H2Bpz) respectively in the presence of NH3, of which 1 was revealed to be a planar trimer and 2 a three-dimensional framework, presenting a rare 3-connected binodal (6(2).10)(6.10(2)) topology and eight-fold interpenetration.

Ligand-controlled mixed-valence copper rectangular grid-type coordination polymers based on pyridylterpyridine.

Six mixed-valence Cu(I)Cu(II) compounds containing 4'-(4-pyridyl)-2,2':6',2' '-terpyridine (L1) or 4'-(2-pyridyl)-2,2':6',2' '-terpyridine (L2) were prepared under the hydrothermal and ambient conditions, and their crystal structures were determined by single-crystal X-ray diffraction. Selection of CuCl(2).2H(2)O or Cu(CH(3)COO)(2).H(2)O with the L1 ligand and NH(4)SCN, KI, or KBr under hydrothermal conditions afforded 1-dimensional mixed-valence Cu(I)Cu(II) compounds [Cu(2)(L1)(mu-1,1-SCN)(mu-Cl)Cl](n) (1), [Cu(2)(L1)(mu-I)(2)Cl](n) (2), [Cu(2)(L1)(mu-Br)(2)Br](n) (3), and [Cu(2)(L1)(mu-1,3-SCN)(2)(SCN)](n)(4), respectively. Compound 5, prepared by layering with CuSCN and L1, is a 2-dimensional bilayer structure. In compounds 1-5, the L1 ligand and X (X = Cl, Br, I, SCN) linked between monovalent and divalent copper atoms resulting in the formation of mixed-valence rectangular grid-type M(4)L(4) or M(6)L(6) building blocks, which were further linked by X (X = Cl, Br, I, SCN) to form 1- or 2-dimensional polymers. The sizes of M(4)L(4) units in 1-4 were fine-tuned by the sizes of X linkers. Reaction of Cu(CH(3)COO)(2).H(2)O with L2 and NH(4)SCN under hydrothermal conditions gave mixed-valence Cu(I)Cu(II) compound [Cu(2)(L2)(mu-1,3-SCN)(3)](n) (6). Unlike those in 1-5, the structure of 6 was constructed from thiocyanate groups and the pendant pyridine of L2 left uncoordinated. The temperature-dependent magnetic susceptibility studies on compounds 1 and 4 showed the presence of mixed-valence electronic structure.