An efficient mixed-valence copper pyrazolate catalyst for the conversion of carbon dioxide and epoxides into cyclic carbonates.

In this paper, a cyclic (CuIpz)3·CH3CN (1) precursor and a mixed-valence pentanuclear complex CuI3CuII2(OH)pz6·CH3CN (2) have been synthesized and structurally characterized by single-crystal X-ray diffraction, where pzH = 4-chloro-3,5-diphenylpyrazole. The excellent catalytic activity of 2 has been demonstrated in the chemical fixation of CO2 into value-added cyclic carbonates, which can be carried out at ambient pressure and room temperature along with ultra-high yield and perfect steric hindrance tolerance. Based on density functional theory (DFT) calculations and comparison with the catalytic performance of 1, it is proposed that the coordinatively unsaturated CuII atoms of 2 are probably the active sites for this catalytic reaction.

Fabrication of Two Isomorphic and Hyperstable Rare Earth-Based Metal-Organic Frameworks with Efficient Ratiometric Probe and Photocatalytic Performances.

Two isomorphic lanthanide compounds {[Ln(ddpp)(H2O)]·CH3CN}n (Ln = Eu and Gd, H4ddpp = 2,5-di(2',4'-dicarboxylphenyl)pyridine) were synthesized. Complex 1-Eu displays ultrahigh acid-base stability and thermal stability. Furthermore, luminescence measurements revealed that 1-Eu could detect quinolone antibiotics with an ultralow limit of detection in aqueous solution. The ratiometric probe properties for sensing antibiotics could be attributed to the incompletely sensitized Eu3+ ion of the ligand. Remarkably, it is interesting that 1-Gd exhibits excellent tetracycline degradation properties under visible light. Ultraviolet-visible diffuse reflectance spectroscopy and valence band X-ray photoelectron spectroscopy were carried out to investigate the photodegradation mechanisms. Moreover, a rational explanation for the fluorescent probe and photocatalysis behavior of these two complexes was also discussed with the assistance of density functional theory calculations.

Supramolecular Interactions of Fullerene C60 with 1,3,5-Trifluoro-2,4,6-triiodobenzene: A Combined Theoretical and Experimental Study.

The noncovalent interactions between fullerene C60 and 1,3,5-trifluoro-2,4,6-triiodobenzene (C6 F3 I3 ) have been investigated in detail by means of a combined theoretical and experimental study. The noncovalent interactions formed by C60 with C6 F3 I3 in the gas phase were modeled by means of quantum chemical calculations, and the noncovalent interactions formed between C60 and C6 F3 I3 in the solid state were explored by means of single-crystal X-ray diffraction studies at both low temperature and room temperature. In both the gas phase and solid state, formations of the π⋅⋅⋅π-stacking interactions, halogen bonds, and F⋅⋅⋅π interactions were found in the supramolecular complexes of C60 with C6 F3 I3 . The strength of these noncovalent interactions was characterized by means of dispersion-corrected density functional theory (DFT) calculations, and the nature of these noncovalent interactions was revealed through energy-component analyses.

A four-unit [c2]daisy chain connected by hydrogen bonds.

A mono-adenine-functionalized pillar[5]arene and a guest including uracil were prepared. They formed a novel four-unit [c2]daisy chain both in the solid state and in a chloroform solution. As far as we know, this [c2]daisy chain is the first one without a covalently bound linear thread. This unique assembly behavior is mainly induced by hydrogen-bond interactions between A and U in the A-U base pairs.

A series of lanthanide-organic polymers incorporating nitrogen-heterocyclic and aliphatic carboxylate mixed-ligands: structures, luminescent and magnetic properties.

Seven new lanthanide-organic coordination polymers incorporating both nitrogen heterocyclic dicarboxylate and various auxiliary ligands, {[Ln(3)(Hpimda)(4)(mu(2)-HCOO).5H(2)O].H(2)O}(n)} Ln = Sm (1), Ln = Eu (2), Ln = Gd (3), Ln = Dy (4), Ln = Ho (5), {[Ce(2)(Hpimda)(2)(mu(4)-C(2)O(4)).8H(2)O].2H(2)O}(n) (6), {[Yb(2)(pyda)(mu(4)-C(2)O(4))(2).4H(2)O].3H(2)O}(n) (7) (H(3)pimda = 1H-2-propyl-4,5-imidazoledicarboxylic acid, H(2)pyda = 2,6-pyridinedicarboxylic acid) have been fabricated successfully and characterized systematically. Complexes 1-5 are isomorphous and isostructural, and are built from two-dimensional (2-D) double-decker networks based on the tetranuclear basic carboxylate as a secondary building unit (SBU). Both polymers 6 and 7 feature a (3,4)-connected 3-D framework consisting of 2-D lanthanide-organic hexagonal grids, which are further interlinked via the mu(4)-oxalate ligand. The results of magnetic determination show the same end-to-end bridging fashion of formate group results in different magnetic properties occurring between lanthanide centers. The luminescence emission spectra of the complexes vary depending on the lanthanide ion present.

Self-assembly of a series of cobalt(II) coordination polymers constructed from H2tbip and dipyridyl-based ligands.

A series of interesting Co(II)-H(2)tbip coordination polymers incorporating different auxiliary ligands, {[Co(tbip)(bipy)(H(2)O)(3)] x 0.5(bipy) x H(2)O}(n) (1), [Co(tbip)(bipy)](n) (2), {[Co(3)(tbip)(3)(dpe)(3)] x 0.5(dpe) x 3 H(2)O}(n) (3), [Co(2)(tbip)(2)(dpe)(H(2)O)](n) (4), [Co(2)(tbip)(2)(bpa)(H(2)O)](n) (5), and {[Co(2)(tbip)(2)(bpa)(2)] x 2.5 H(2)O}(n) (6) (H(2)tbip = 5-tert-butyl isophthalic acid; bipy = 4,4'-bipyridine; dpe = 1,2-di (4-pyridyl)ethylene; bpa = 1,2-bi(4-pyridyl)ethane) were synthesized. X-ray structural analyses of 1-6 reveal a diverse range of structures, ranging from 1D (1) to 2D (2, 6) to 3D (3, 4, 5). Complex 1 shows 1D zigzag bipy-bridged polymeric chains with the terminal tbip ligands as pendants, which are extended to a 3D hydrogen-bonded supramolecular framework involving 1D open channels which encapsulate guest bipy molecules. Polymers 2 and 6 feature similar 2D infinite layer frameworks consisting of cobalt dimers. The structure of 3 is constructed from [Co(2)(tbip)(2)](n) layers, which consists of alternating left- and right-handed helical chains, and further pillared by dpe ligands into a 3D six-connected self-penetrating 4(8).6(6).8 network. The prominent cavities in 3 are parallel to the (101) plane and encapsulate free dpe as guest molecules. Polymers 4 and 5 are isostructural, showing 2-fold interpenetrating 3D alpha-Po networks constructed from binuclear cobalt nodes. The thermal stabilities and X-ray powder diffraction studies indicate that the framework of 3 can keep stable after the loss of guest molecules. Studies of the magnetic susceptibilities of 2-6 reveal weak antiferromagnetic exchange interactions between adjacent Co(II) centers.

Bis(1,3,4-thia-diazol-2-yl) disulfide.

The title compound, C(4)H(2)N(4)S(4), lies about a twofold rotation axis situated at the mid-point of the central S-S bond. Each of two thia-diazole rings is essentially planar, with an rms deviation for the unique thia-diazole ring plane of 0.0019 (7) Å. C-H⋯N hydrogen bonds link adjacent mol-ecules, forming zigzag chains along the c axis. In addition, these chains are connected by inter-molecular S⋯S inter-actions [S⋯S = 3.5153 (11) Å] , forming corrugated sheets, and further fabricate a three-dimensional supra-molecular structure by inter-molecular N⋯S contacts [S⋯N = 3.1941 (17) Å].

Aqua-(2,9-dimethyl-1,10-phenanthroline-κN,N')bis-(2-hydroxy-benzoato-κO)manganese(II) 2,9-dimethyl-1,10-phenanthroline hemisolvate.

In the asymmetric unit of the title complex, [Mn(C(7)H(5)O(3))(2)(C(14)H(12)N(2))(H(2)O)]·0.5C(14)H(12)N(2), the Mn(II) ion is coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) mol-ecule, one water mol-ecule and two monodentate 2-hydroxy-benzoate anions in a distorted trigonal-bipyramidal geometry. The OH group of the 2-hydroxy-benzoate anion is disordered over two positions with site-occupancy factors of 0.5. The asymmetric unit is completed with by an uncoordinated half-mol-ecule of dmphen, disordered about a crystallographic twofold axis. In the crystal structure, mol-ecules are linked into a two-dimensional framework by O-H⋯N, O-H⋯O and C-H⋯O hydrogen bonds. The packing of the structure is further stabilized by π-π stacking inter-actions involving dmphen mol-ecules, with centroid-centroid separations of 3.8027 (3) and 3.6319 (3) Å.

Poly[dichloridobis(µ(2)-di-4-pyridyl sulfide-κN,N')cobalt(II)].

In the title compound, [CoCl(2)(C(10)H(8)N(2)S)(2)](n), the Co(II) atom is located on an inversion centre and is six-coordinated by four N atoms of four symmetry-related di-4-pyridyl sulfide ligands, and two Cl atoms in trans positions, in a distorted octa-hedral geometry. The bridging bidentate di-4-pyridyl sulfide ligands link the Co(II) centres into a three-dimensional network. The four coordinating pyridine groups are donors and acceptors (N atoms) for intra-molecular C-H⋯N and C-H⋯Cl hydrogen bonds.

Poly[[tris-[µ-2,2'-(butane-1,4-diyl-dithio)bis-(1,3,4-thia-diazole)-κN:N]copper(II)] bis-(perchlorate)].

In the title compound, {[Cu(C(8)H(10)N(4)S(4))(3)](ClO(4))(2)}(n), the Cu(II) atom is located on a threefold inversion axis coordinated by six N atoms of symmetry-equivalent 2,2'-(butane-1,4-diyl-dithio)bis-(1,3,4-thia-diazole) ligands in a slightly distorted octa-hedral geometry. Adjacent Cu(II) atoms are linked by the bridging bidentate thia-diazole ligands, which are situated about inversion centers. This leads to the formation of a three-dimensional network structure.

catena-Poly[[[bis-[2,2'-(propane-1,3-diyl-dithio)bis-(1,3,4-thia-diazole)-κN]copper(II)]-bis-[µ-2,2'-(propane-1,3-diyldithio)bis-(1,3,4-thia-diazole)-κN:N]] bis-(perchlorate)].

In the title compound, {[Cu(C(7)H(8)N(4)S(4))(4)](ClO(4))(2)}(n), the Cu(II) atom, occupying a crystallographic inversion centre, is six-coordinated by six N atoms of three symmetry-related 2,2'-(propane-1,3-diyldithio)bis-(1,3,4-thia-diazole) (L) ligands in a slightly distorted octa-hedral geometry. The ligand L adopts two kinds of coordination modes in the crystal structure; one is a monodentate coordination mode and serves to complete the octa-hedral coordination of the Cu atom and the other is an N:N'-bidentate bridging mode in a trans configuration, bridging Cu atoms via translation symmetry along the b axis into a chain structure. The perchlorate ions serve as acceptors for inter-molecular C-H⋯O hydrogen bonds, which link the chains into a three-dimensional network.

Poly[[bis-(acetonitrile-κN)bis-[µ(2)-2,2'-(methyl-enedithio)bis-(1,3,4-thia-diazole)-κN:N]copper(II)] bis-(perchlorate) acetonitrile solvate].

In the title compound, {[Cu(C(5)H(4)N(4)S(4))(2)(C(2)H(3)N)(2)](ClO(4))(2)·C(2)H(3)N}(n), the Cu(II) atom occupies a crystallographic inversion centre and is six-coordinated by six N atoms of four symmetry-related 2,2'-(methyl-enedithio)bis-(1,3,4-thia-diazole) (L) ligands and two acetonitrile mol-ecules in a slightly distorted octa-hedral geometry. The ligand L adopts an N:N'-bidentate bridging mode in a trans configuration, bridging the Cu atoms via translation symmetry, forming a two-dimensional layer-like structure. The perchlorate ions serve as acceptors for inter-molecular C-H⋯O hydrogen bonds, which link the layers into a three-dimensional network. The ClO(4) (-) anion is disordered with an occupation ratio of 0.658:0.342.

Poly[µ(2)-chlorido-(µ(2)-3H-1,3,4-thia-diazo-lium-2-thiol-ato-κS:S)silver(I)].

In the title compound, [AgCl(C(2)H(2)N(2)S(2))](n), the Ag(I) ion has a distorted tetra-hedral geometry, defined by two S atoms of two symmetry-related 1,3,4-thia-diazo-lium-2-thiol-ate ligands and two chloride ions. The Ag(I) ions are bridged into a two-dimensional network parallel to the ab plane by chloride ions and thia-diazole ligands. In the network, the Ag(I) ions are separated by 4.0316 (12) Šalong the a axis and by 4.8822 (13) Šalong the b axis. N-H⋯Cl hydrogen bonds are observed within the network.

Di-µ-chlorido-bis-{[2-(2-pyridylmethyl-amino)ethanesulfonato-κN,N',O]copper(II)}.

In the title compound, [Cu(2)(C(8)H(11)N(2)O(3)S)(2)Cl(2)], the Cu atoms are five-coordinated in a distorted square-pyramidal geometry by three donor atoms of the deprotonated anionic 2-(2-pyridylmethyl-amino)ethanesulfonate (pmt) ligand and two Cl atoms. The Cl atoms bridge two Cu atoms, giving a binuclear structure; the centroid of the Cu(2)Cl(2) ring lies on a crystallographic center of inversion. The complex is stabilized by hydrogen bonds and π-π stacking inter-actions [average inter-planar distance = 3.4969 (1) Šand ring-centroid separation distance = 4.1068 (4) Å].

catena-Poly[[[diaqua-lanthanum(III)]-tetra-kis[µ-N-(4-acetamido-phenyl-sulfon-yl)-glycinato]-[diaqua-lanthanum(III)]-bis-[µ-N-(4-acetamido-phenyl-sulfon-yl)-glycinato]] 4,4'-bipyridine disolvate tetra-deca-hydrate].

In the title compound, {[La(2)(C(10)H(11)N(2)O(5)S)(6)(H(2)O)(4)]·2C(10)H(8)N(2)·14H(2)O}(n), the La(III) ions are in a slightly distorted bicapped trigonal prismatic geometry, and are linked by six carboxyl-ate groups in a syn-syn bidentate bridging fashion to form a one-dimensional inorganic-organic alternating linear chain. These polymeric chains generate microchannels extending along [100], and these cavities are occupied by discrete tetra-deca-meric water clusters, which inter-act with their surroundings and finally furnish the three-dimensional supra-molecular network via 15 O-H⋯O, one O-H⋯S, two O-H⋯N and six N-H⋯O classical hydrogen bonds. 4,4-Bipyridine acts as an inserting component and hydrogen-bond acceptor, and it is a nonplanar mol-ecule with a dihedral angle of 33.12 (13)° between the pyridine rings. Owing to the numerous classical hydrogen bonds, the observed weak inter-molecular C-H⋯O, C-H⋯π and π-π stacking inter-actions can be neglected with regard to stabilizing the network.

Di-4-pyridyl sulfide-isophthalic acid (1/1).

In the heteromolecular title structure, C(10)H(8)N(2)S·C(8)H(6)O(4), the two components are linked by O-H⋯N hydrogen bonds to form a one-dimensional chain. These chains are further inter-connected by weak inter-molecular C-H⋯O hydrogen bonds and weak C-H⋯π inter-actions to generate a three-dimensional supra-molecular structure.

1,3-Di-4-pyrid-ylpropane-2-hydroxy-benzene-1,4-dicarboxylic acid (1/2).

In the title compound, C(13)H(14)N(2)·2C(8)H(6)O(5), which crystallized in the monoclinic C2/c space group, the 1,3-bis-(4-pyrid-yl)propane mol-ecules and 2-hydr-oxy-1,4-benzene-dicarboxylic acid mol-ecules are alternately linked by O-H⋯N and O-H⋯O hydrogen bonds into herringbone/zigzag chains.

4-(2-Carboxy-benzo-yl)benzoic acid-4,4'-bipyridine (1/1).

In the heteromolecular title compound, C(15)H(10)O(5)·C(10)H(8)N(2), the two components are linked by O-H⋯N hydrogen bonds to form four-component ring supra-molecular assemblies. These are further inter-connected with neighbouring mol-ecules by weak inter-molecular C-H⋯π inter-actions and C-H⋯O hydrogen bonds to generate a three-dimensional network.

catena-Poly[[bis-(nitrato-κO,O')copper(II)]-µ-2,2'-(ethane-1,2-diyldithio)di-1,3,4-thia-diazole-κN:N].

In the title compound, [Cu(NO(3))(2)(C(6)H(6)N(4)S(4))](n), the Cu(II) atom, occupying a crystallographic inversion centre, is six-coordinated by two N atoms of two 2,2'-[1,2-ethane-diyl-bis-(thio)]bis-[1,3,4-thia-diazole] ligands in trans positions, and four O atoms from two symmetry-related opposite nitrate anions, which are asymmetrically bonded, resulting in a strong distorted octa-hedral geometry of the central atom. The ethane group is equally disordered over two sites via another inversion centre. The bridging bidentate 2,2'-[1,2-ethanediylbis(thio)]bis-[1,3,4-thia-diazole] ligands link the Cu(II) centres into a one-dimensional chain. The chains are inter-connected via inter-molecular S⋯O inter-actions [3.044 (4) and 3.084 (5) Å] and weak C-H⋯O hydrogen bonds, generating a three-dimensional supra-molecular structure.