Search

Two new tungsten oxide clusters compounds on Na1, and through the OW16···O7 (2.988A) hydrogen bond connect into a three-dimensional network structure. We conducted infrared tests, thermogravimetric tests and two-dimensional infrared correlation spectroscopy tests on compounds 1 and 2, and set up control experiments to test the inhibitory effects of two compounds on two common pathogenic bacteria E. coli and Staphylococcus aureus in life, combined with two-dimensional infrared correlation spectroscopy (2D-IR COS) and thermogravimetric analysis, the sandwich-type compound 1 and compound 2 with the same configuration, the polarizability of Mn and Cu have a greater impact on the overall configuration, which may be directly lead to the different antibacterial effects of the both. Experimental tests and analysis show that the transition metals in the compound have a close influence on the inhibition of S. aureus.

Two polyoxometalate-phosphonate compounds with the formular (TBA)2(Hbiz)2 [(C3H5O2P)2Mo5O21]•05H2O (1) and [Ni(2,2′bpy)3]2[(C6H5P)2Mo5O21]•3H2O (2) (TBA=tetrabutylammonium, biz=benzimidazole, bpy=bipyridine) have been synthesized under hydrothermal condition and structurally determined by single-crystal X-ray diffraction. Compound 1 and 2 are Strandberg-type polyoxometalate. The compounds were characterized by various means containing elemental analysis, PXRD, IR and thermal gravimetric analysis. Additionally, their photocatalytic degradation properties toward rhodamine-B are investigated. Compound 2 as catalyst has higher photocatalytic degradation of RhB than 1 due to its larger porosity. Results of the experiment on antitumor activities in vitro showed that two compounds inhibited five different human cancer cells (gastric cancer cells, HGC-27 and SNU668; liver cancer cells, Huh7; and colon cancer cells, HCT116 and SW480) demonstrated dose dependency and selectivity. The relationship between structure and biology activity indicate that inorganic and organic segments may influence the antitumor activity, the introduction of biz and 3-phosphonopropionic acid into P2Mo5 can make compound 1 better antitumor activities.

An organo-bismuth benzoate with phen as auxiliary ligand, [Bi(phen)(C 6 H 5 COO)(C 6 H 4 COO)] ( 1) (phen = 1,10-phenanthroline) has been hydrothermally synthesized from bismuth nitrate, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, PXRD, IR spectra, TG analyses, temperature-depended 2D-IR COS (two-dimensional infrared correlation spectroscopy). Interestingly, benzoate anions in 1 came from the desulfuration reaction of 2-mercaptonbenzoic acid under hydrothermal condition. Compound 1 is a discrete organo-bismuth compound with benzoate and phen ligands. The offset face-to-face π - π stacking interactions and C–H⋯O hydrogen bonds link the isolate complex into a 3D supramolecular network. The temperature-depended 2D-IR COS indicates that the stretching vibrations of C C/C N of aromatic rings and C O bonds are sensitive to the temperature change.

Two novel polyoxovanadoborates with the similar vanadium cage but different number of ligand have been hydrothermally synthesized, namely (enH2)6[V12B18O58(OH)2(H2O)0.5] 12H2O and (enH2)10[V12B18O56(OH)4(H2O)]2 16H2O. The structure of 1 and 2 was determined by single crystal X-ray diffraction. Both compounds are connected to form a supramolecular structure through hydrogen bonding. But the number of free ethylenediamine molecules outside the cage of the two compounds is different, and so is the pilling way stacked by hydrogen bonding. We use two-dimensional infrared correlation spectroscopy (2D IR COS), thermogravimetry (TG), and high temperature infrared (HTIR) to study the effect of hydrogen bonding on the thermal stability for two compounds. From the two-dimensional infrared correlation spectrum, it can be seen that the response peaks of νs(V-Oμ), νas(V-Oμ), νs(V=Ot), νas(V=Ot), νas(Ba–O) and νas(Bb-O) of the two compounds are different, which may be caused by the different connection modes between the weak interaction forces of the two compounds. The analysis results of TG and HTIR curves are consistent with the 2D IR COS. Three characterization methods show that hydrogen bonding can not only increase the initial temperature of organic functional groups and crystal water decomposition, but also greatly affect the temperature at which cluster cages begin to decompose. 2D-IR COS provides an effective new method for studying hydrogen bonding.

A sandwich-type polyoxotungstate, {[Na(H2O)2]H8[KNa2(H2O)6][Cu(H2O)]3(SbW9-O33)2}n⋅4nH2O⋅4n(tn) (1) (tn = 1,3-Propanediamine) has been synthesized and characterized by IR, UV-DRS, single-crystal X-ray diffraction analysis, TGA, XPS, magnetic-dependent 2D-IR correlation spectroscopy (2D-COS IR). The Herve-type polyanion {[KNa2(H2O)6][Cu(H2O)]3(SbW9O33)2}9− of compound 1 consists of two trivacant Keggin moieties [SbW9O33]9− which are linked by three Cu2+ ions, and the space between the three Cu2+ ions is occupied by two sodium ions and one potassium ion forming a six-membered ring, and resulting in the polyanion with C2v symmetry. Compound 1 exhibits a 1D ribbon-like structure in which the adjacent polyanions were connected by the K+ in the central belt and Na+, which is rarely reported for Herve-type polyanion. The magnetic-dependent 2D-IR correlation spectroscopy display obvious magnetic response signal of the groups which Cu2+ ions attached to.

Two metal–organic β-octamolybdate supported compounds containing nitrogen-heterocyclic ligands, [Co(dpq)2 H2O]2[β-Mo8O26] 0.5H2O 1, (H3biim)4[β-Mo8O26] 2 (dpq = 1,10-phenanthroline-5,6-dione; H2bimm = 2,2′-biimidazole), have been hydrothermally synthesized and characterized by X-ray crystal structural analysis, elemental analysis, IR spectrum, UV–VIS DRIS, 2D-IR COS (two-dimensional infrared correlation spectroscopy), PXRD, TG analysis, simulated IR spectrum and theoretical calculations from HOMO–LUMO. X-ray crystal structural analyses reveal that compound 1 has the 1-D supramolecular structure, which is formed via hydrogen bonds between water molecules coordinated to Co2+. In compound 2, the 2-D supramolecular structure is built by aromatic–aromatic stacking interactions and H-bonds between ligands. Simulated IR spectra gained by quantum calculation are used for structure discussion, which is the first time that simulated IR results are used to reveal the relationship between bond vibrations of β-octamolybdate compounds and their related IR peak responses. Additionally, by using 2D-IR COS, structural properties like thermal and magnetic sensitivities have also been analyzed.

Three rare earth compounds with 3-methylbenzoic acid (HMeBA) have been hydrothermally synthesized directly: Gd 2 (MeBA) 6 (o-Phen) 2 1 (o-Phen = o-phenanthroline), [Gd 2 (MeBA) 6 (2,2′-bpy)] n 2 (2,2′-bpy = 2,2′-bipyridine) and Gd (MeBA) 3 ·(4,4′-bpy) 0.5 3 (4,4′-bpy = 4,4′-bipyridine). These crystal structures were determined by single-crystal X-ray diffraction with the following data: 1 : monoclinic, Cc ; 2 : monoclinic, P 2 1 / n ; 3 : Triclinic, P − 1. The compound 1 is a zero-dimensional Bi-nuclear oligomer and ligand -o- phenanthroline participates in the coordination; the compound 2 is a one-dimensional chain and the second ligand -2,2′-bpy participates in coordinating with the Gd ion; in particular, due to the existence of the second ligand -4,4′-bpy which acts as the bridge, the compound 3 is the two-dimensional layer. Additionally, in order to explore the structural characteristic, photo-luminescent and the 2D-IR correlation spectroscopy containing the temperature-induced structural variations and magnetism-induced structural variations are used.

By employing hydrothermal method, we identify a new organically templated aluminoborate [NH 0.5 C 4 H 4 NH 0.5 ][AlB 12 O 14 (OH) 12 ] which is structurally determined by single crystal X-ray diffraction and characterized by simulated and experimental IR, 2D IR COS (two-dimensional infrared correlation spectroscopy), NICS (nucleus-independent chemical shifts) and Mulliken charges calculations. Although the cluster anions [AlB 12 O 14 (OH) 12 ] − is identical to the counterpart of compound reported by Lin et al. at 2008, we firstly bring up its quasi-aromaticity, discuss and confirm it by NICS, Mulliken charges calculations and magnetic-induced 2D IR COS, and conclude that three isolated and non-coplanar four-center six-electron π bonds of cluster could cooperate and interact with each other to form a closed conjugated large π orbital system, endowing the cluster anions with quasi-aromaticity. Thus, a one-dimensional chain is constructed by π – π stacked interaction between quasi-aromatic clusters and aromatic pyrazine along [ 1 0 ¯ 1 ] direction. The title compound crystallizes in monoclinic space group C2/c with a = 18.397(4), b = 12.0670(16), c = 11.075(2) A, α = 90.00, β = 116.483(11), γ = 90.00°, Z = 4, V = 2200.6(7) A, R = 0.0442 and wR = 0.1128 for 2689 observed reflections.

Three rare-earth complexes with 3-methylbenzoic acid (HL) have been hydrothermally synthesized directly: Yb(C8H7O2)3 1 and Ln(C8H7O2)3·(4,4′-bipy)0.5 (Ln = Eu 2, Gd 3) (4,4′-bipy = 4,4′-bipyridine).The crystal structures were determined by single crystal X-ray diffraction with the following data: 1: monoclinic, P21/n, a = 13.574(3), b = 8.0438(2), c = 20.652(4) A, β = 96.14(3)°; 2: triclinic, P-1, a = 8.1788(2), b = 12.952 (3), c = 12.968(3) A, α = 94.400(3)°, β = 92.260(4), γ = 101.360(4); the complex 1 is a one-dimensional chain. However, due to the existence of the second ligand-4,4′-bipy, the complexes 2 and 3 are a two-dimensional layer, the Lanthanide contraction makes the difference of the structure between the complexes at the same time. Additionally, in order to explore the structural characteristic, the 2D-IR correlation spectroscopy containing the temperature-induced structural variations and magnetism-induced structural variations is used. Photo-luminescent properties of 1 and 2 are discussed in detail.

A novel D3T derivative, 5-amino-4-cyano-3H-1,2-dithiole-3-thione (compound 1) has been obtained in one-pot reaction. The crystal is orthorhombic, space group Pbca, with a = 10.3667(4) A, b = 10.8898(4) A, c = 11.4942(5) A, V = 1297.60(9) A3, and Z = 8. In the crystal, molecules are firstly self-assembled into a complex sheet parallel to the (0 0 1) plane containing centrosymmetric R 2 4 (16) and R 4 4 (24) rings, and then the interconnection of molecular sheets through S···S interactions forms a three-dimensional supramolecular assembly. The DFT calculations are performed for isolated molecule using the B3LYP/6-31+G(d,p) methods. The frontier orbital properties of compound 1 have been reported and discussed. Moreover, a detailed assignment of the fundamental vibrational modes is proposed on the basis of the calculated results.

Two-dimensional correlation infrared spectroscopy (2D-COS) were employed to investigate temperature-dependent spectral variations [(PO 4 ) 2 Mo 5 O 15 ] 6− , β-[Mo 8 O 26 ] 4− , [PMo 12 O 40 ] 3− , [P 2 W 18 O 60 ] 6− cluster anions. Two-dimensional correlation spectra in 800–1000 cm −1 region provides information about the variations of the terminal Mo O bonds in the polyoxomolybdenum (or Polyoxotungstic) cluster anions. In 600–800 cm −1 region, it reveals the information about the variations of the bridging Mo O Mo bonds in the cluster anions. The results indicated that the intensity change of the terminal Mo O bonds are more sensitive than the bridging Mo–O–Mo bands to the temperature variation. Furthermore, from [(PO 4 ) 2 Mo 5 O 15 ] 6− , β-[Mo 8 O 26 ] to [PMo 12 O 40 ] 3− , with the cluster anions becoming larger, the 2D-IR spectra showed the bridging Mo–O–Mo bonds in the cluster anions were becoming more sensitive to temperature variation.

A novel one-dimensional polyoxovanadium borate (H3NCH2CH2NH3)3[(VO)12O4{B8O17(OH)4}2{Na(H2O)}2]·(H3O)2(H2O)6.5 (1) has been synthesized by the hydrothermal method and the structure determined by X-ray crystallography. The structure consists of a continuous contorted V12 ring, constructed from edge-sharing VO5 square pyramids. Two {B8O17(OH)4}14− polyborate chains fill in the cavities formed by the V12 ring. The [(VO)12O4{B8O17(OH)4}2]12− clusters are connected by unusual binuclear Na+ units into 1D chains. The binuclear Na+ units are formed by two neighboring sodium atoms sharing two μ2–O from B–O–B. Each sodium atom is in a distorted octahedral geometry. Other characterizations are also described by elemental analysis, thermal analysis and IR, EPR spectra.