Search

X-ray crystallography reveals four isostructural lanthanide polymeric solids, [Ln2(atp)3(H2O)2]·dmf·4H2O (atp = 2-aminoterephthalate; dmf = N,N′-dimethylformamide; Ln = La (1), Ce (2), Pr (3) and Nd (4), respectively) that are obtained from the solvothermal synthesis which are crystallized in an interesting 3D polymeric framework with a (4,4,6)-linked {42·84}{44·62}2{48·66·8}2 fsy net topology. Upon excitation at 350 nm, they all show the solid state ligand-centered luminescences but both 2 and 3 also exhibit the weak lanthanide-based characteristic emissions in the visible region at room temperature. The cyclic voltammetric investigation indicates that 2 exhibits appreciable electrochemical activity for formaldehyde.

Two new metal–terephthalate polymeric solids, {[Ph4P]2[Cd2(tp)2(Htp)2(H2O)]·3H2O}n (1) and {[Ph4P][Zn(tp)(Htp)]·2H2O}n (2) (tp = terephthalate, [Ph4P] = tetraphenylphosphonium), are obtained from similar hydrothermal synthesis reactions. Upon the template effect of large bulky [Ph4P]+ cation, the d10 transition metal centers are bridged by tp ligands to form an interesting 2D undulating lamellar host network for 1 and a 2D square-grid lamellar host network for 2, respectively. Both compounds exhibit intense fluorescent emission bands at 434 nm (λexc = 333 nm) for 1 and 420 nm (λexc = 350 nm) for 2 in the solid state at room temperature.

Two sandwich-like frameworks with Ag(I) and mixed ligands, [Ag3(bpp)3(ctc)·16H2O]n (1) and [Ag3(bpe)3(btc)·12H2O]n (2) (where bpp = 1,3-bis(4-pyridyl)propane, H3ctc = 1,3,5-cyclohexanetricarboxylic acid, bpe = 1,2-bis(4-pyridyl)ethane, and H3btc = 1,2,4-benzenetricarboxylic acid), have been synthesized and structurally characterized. Fully deprotonated tricarboxylate ctc3 − in 1 or btc3 − in 2, serves as anionic template driving more water molecules to aggregate into different morphologies of polymeric clusters. In 1, the hydrogen-bonding association of sixteen lattice water molecules leads to the formation of 2D layered water, which is composed of three kinds of units including planar (H2O)4, ladder-like (H2O)8 and windmill-shaped (H2O)20 cluster. One novel 1D double-comb-like water aggregate constructed from alternating (H2O)22 cluster and water dimmer exists in 2. The present observations suggest that anionic templates with more carboxylate groups have high tendency of being hydrated and make polymeric clusters possible.

A novel 2D cobalt(II) coordination polymer comprising left- and right-handed helical chains, {[H2bpp][Co2(bpp)2(Hbtec)2(H2O)4]·(H2O)5}n (1) (bpp = 1,3-bis(4-pyridyl)-propane and H4btec = 1,2,4,5-benzenetetracarboxylate), was prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction method. Complex 1 provides suitable hydrophilic channel in which lattice water molecules accumulate, forming a (H2O)5 helicate, stabilized by anchoring to the host structure through hydrogen-bonding interactions involving alternating water molecules and the carboxylate oxygen atoms of Hbtec3− ligands.

A mixed-ligand Ag(I) coordination polymer {[Ag2(bpe)2(H2O)2](chd)·5H2O}n (1) (bpe = 4,4′-bipyridylethylene, H2chd = 1,4-cyclohexanedicarboxylic acid), has been synthesized and structurally characterized. Complex 1 exhibits a three-dimensional (3-D) supramolecular sandwich architecture that is composed of cationic chains of Ag(I) ions and bpe ligands, alternating with anionic sheets in which uncoordinated chd2 − anions and water molecules form a 2-D hydrogen-bonded network. An odd-numbered (H2O)7 cluster is trapped inside the water-chd aggregation. The discrete water heptamer consists of a puckered pentameric core and two pendent water molecules and structurally shows similarity to the simple hydrocarbon (1,1)-dimethylcyclopentane.

The ultrasonic reaction of Ag2O, 1,3-bis(4-pyridyl)propane (bpp) and Na2B4O5(OH)4·8H2O (borax) under ammoniacal medium gave rise to an unexpected 3D Ag(I) supramolecular sandwich lamellar framework, {[Ag2(bpp)2(H2O)2]·[(H3BO3)3(CO3)·2H2O]}n (1), which consists of 2D silver-bpp cationic host and water–borate–carbonate anionic guest layers. The present 2D anionic layer is formed by fused H2O–H3BO3–CO32 − anionic rosette ribbons, in which H3BO3 is obtained via in situ hydrolysis of borax and CO32 − derived from absorption of CO2 in air. Interestingly, an unprecedented [CO32 −·3(H3BO3)] hydrogen-bonding aggregate having the shape of one concave three-leaved propeller is found in the anionic rosette ribbon.

Mercaptotin complexes are difficult to synthesize since they are usually transient intermediates. Here, we report the synthesis and crystal structure of two examples of stable hexamercaptotin complexes [N(CH 3 ) 4 ] 2 Sn(SH) 6 ( 1 ) and [N(C 2 H 5 ) 4 ] 2 Sn(SH) 6 ( 2 ), and discuss their stability by use of quantum chemistry method. Both the complexes 1 and 2 were obtained by hydrothermal synthesis and were crystallized in monoclinic space group, C2/m, Z =8, a =25.724(8), b =18.183(6), c =9.097(3) for 1 , and C2/c, Z =4, a =14.0733(14), b =14.4018(14), c =13.2538(13) for 2 . Single crystal X-ray diffraction analysis revealed that the Sn(IV) centers of 1 and 2 are octahedrally coordinated to six [SH] − ligands and all of the six hydrosulfuryl groups are located in terminal positions. The computational results of quantum chemistry method show that highly symmetric coordination of [SH] − ligands can be effective in stabilizing stannanethiols entities.

A cadmium benzenetricarboxylate coordination polymer has been synthesized by hydrothermal reaction. It presents an interesting tri-layer structure motif featuring tri-nuclear units and exhibits intense photoluminescence as well.

Two Cd(II)-pyridinedicarboxylate polymers have been synthesized by hydrothermal reaction. They present novel structural motifs and exhibit intense fluorescent emissions upon photoexcitation.

A phosphatooxalate compound {Na2[Zn(C2O4)1.5H2PO4] · 2H2O}n 1 was synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction, IR spectroscopy, thermal gravimetric analysis (TGA) and fluorescent spectroscopy. X-ray single-crystal analysis revealed that its structure was a new mixed inorganic–organic ligand supramolecular framework building up through multilayer assembly.

The first octanuclear tin(IV)–oxosulfide complex (NH 4 ) 2 (Et 4 N) 4 [Sn 8 S 12 O 4 (SPh) 6 ] has been synthesized by mixing stoichiometric amount of Sn(SPh) 4 and (NH 4 ) 2 WOS 3 and thiophenol in DMF. The compound was crystallized in orthorhombic space group Cmcm, Z=4, a=18.0463(4) A , b=15.7599(2) A , c=19.1914(5) A , a single crystal X-ray diffraction analysis revealed two coordinate modes of the tin atoms: five-coordinated distorted rectangular pyramid SnOS 4 and six-coordinated octahedron SnO 3 S 3 .

The cyanide act as a bridging ligand between metal atoms and it usually gives to polymeric compound with 2D or 3D networks, two novel heterometallic polymers containing CN ligands {[Et4N]2[WS4Cu4(CN)2Br2]}n (1) and [ZnCu4(CN6(dmf)4]n (2) have been synthesized and characterized in this paper.

Due to a revision in the experimental method the authors of above paper would like to correct wrongly refined structures. Explanation of fault: In our previous paper entitled “Novel hexamercaptotin: synthesis and characterization of [N(CH3)4]2Sn(SH)6 and [N(C2H5)4]2Sn(SH)6 complexes” in Inorganic Chemistry Communications, 2001, 4, 643–647, the following two errors were made in solving the structures