Synthesis,Crystal Structure and Optical and Photocatalytic Properties of a Discrete Cuprous Iodide Compound with a Transition Metal Complex Cation

With transition metal complex, a discrete cuprous iodide compound, namely, [Ni（phen）3]2Cu6I10（1, phen = 1,10-phenanthroline） has been solvothermally synthesized and structurally characterized. Single-crystal X-ray diffraction studies revealed that compound 1 crystallizes in triclinic space group P1（No. 2） with a = 11.2694（2）, b = 12.3699（3）, c = 15.0387（3） ？, α = 102.840（2）, β = 105.215（2）, γ = 96.388（2）°, V = 1940.04（7） ^3, Z = 1, Dc = 2.438 g·cm^-3, F（000） = 1324, R = 0.0256 and w R = 0.0555（I 〉 2σ（I））. Compound 1 features a discrete anionic moiety of [Cu6I10]^4- charge-balanced by two metal complexes of [Ni（phen）3]2＋. The optical absorption edge of compound 1 was estimated to be 2.24 eV. Interestingly, nearly 95% of contaminant（crystal violet aqueous solution（CV）, 50 m L, 1.0 × 10^-5 M） could be decolorized after exposure to visible light within 30 min, illustrating an impressive photocatalytic activity of compound 1. The thermal stability of 1 has also been studied.

Preparation and Crystal Structure of Hetero-metal Clusters [η~5-C_5H_4C(O)CH_2CH_2C(O)OCH_3]FeCoM(μ_3-S)(CO)_8 (M = Mo or W)

The hetero-metal clusters [■5-C5H4C（O）CH2CH2C（O）OCH3]FeCoM（■3-S）（CO）8 （M = Mo 1, M = W 2） were prepared by thermal reactions of FeCo2（CO）9(（3-S） with metal exchange reagent [■5-C5H4C（O）CH2CH2C（O）OCH3]M（CO）3Na （M = Mo or W） in THF. Cluster 1 reacted with 2,4-dinitrophenylhydrazine at room temperature to yield the cluster hydrazone derivative (（3-S）CoFeMo（CO）8[(5-C5H4C（NR）Me] [R = NHC6H3-2,4-（NO2）2] 3. All the compounds were characterized by elemental analyses, IR and NMR spectra. Cluster 1 was determined by single crystal X-ray diffraction. Crystal data: C18H11O11SCoFeMo, Mr = 646.05, triclinic, space group P, a = 8.148（2）, b = 10.685（3）, c = 13.410（4） ?, ( = 100.077（5）, ( = 102.452（5）, ( = 91.108（6）(, V = 1120.4（5） ?3, Z = 2, Dc = 1.915 g/cm3, F（000） = 636, ( = 2.071 mm(1, the final R = 0.0378 and wR = 0.0968 for 5074 observations with (I > 2（（I））.

Syntheses of Two Chiral Clusters [η~5-C_5H_4C(NR)CH_3]- RuNiM(CO)_5(μ_3-S) (R =NH-C_6H_3-2,4-(NO_2)_2,M=Mo,3;M=W,4) and the Single-crystal Structure of Cluster 3

The new chiral clusters [h5-C5H4C(NR)CH3]RuNiM(CO)5(m3-S) (R = NH-C6H3-2,4- (NO2)2, M = Mo, 3; M = W, 4) were synthesized and the structure of cluster 3 was determined by single-crystal X-ray analysis. Crystal data: C23H16O9N4MoNiRuS, Mr = 780.18, orthorhombic, space group Pbca with the following crystallographic parameters: a = 13.207(4), b = 16.036(5), c = 25.513(8) , Z = 8, V = 5403(3) 3, Dc = 1.918 g/cm3, m = 1.834 mm-1 and F(000) = 3072. The final R = 0.0512 and wR = 0.1132 for 2525 reflections with I > 2.00s(I).

Synthesis and Crystal Structure of Novel Mixed-metal Alkoxide Clusters of Ytterbium and Sodium: Yb_4O_4(O^iPr)_(16)Na_(12)

The mixed-metal cluster Yb4O4（OiPr）16Na12 has been synthesized and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. The crystal belongs to the cubic system, space group P23 with a = b = c = 13.9788（3）A, V = 2731.55（10）A3, Z = 1, Dc = 1.202 g/cm3, Mr = 1977.42,/J = 3.480 mm-1, F（000） = 972, the final R = 0.0288 and wR = 0.1511 for 1677 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that Yb4O4（Oipr）16Na12 is centrosym- metric and the structure contains four ytterbium metals and twelve sodium metals, and each ytterbium atom is coordinated by six oxygen atoms. In addition, an ancillary computational analysis of the optimized molecular unit was provided. The large energy gap （3,31 eV） between HOMO and LUMO indicates that the structure framework is particularly stable.

Synthesis and Structures of A Series of Novel Rare Earth Transition Metal Sulfates

Seven new rare earth transition metal sulfates were synthesized by hydrothermal reactions under conditions slightly above the critical point of water. Their crystal structures were determined from single crystal X-ray data. The compositions of the new compounds can be represented by two general formulae ： REM （OH） 3 （SO4） and RE2M （OH） 3 （SO4） 2F （H2O） with RE = Gd, Tb, Dy ; M = Ni, Cu. Three different crystal structure types were found for the formula REM （OH） 3 （SO4）. The structures of the new compounds all feature infinite chains of REOn coordination polyhedra, which are connected to chains of CuO6 or NiO6 octabedra. The limited size range of the rare earth cations observed in these compounds is most likely because of interactions between the octabedral chains and the chains of REOn polyhedra. The new compounds are closely related to the known yttrium transition metal sulfates.

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

Synthesis and Structural Chemistry of Two Novel Transition Metal Organic Phosphonates

Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.

Pressure-induced phase transition in transition metal trifluorides

As a fundamental thermodynamic variable, pressure can alter the bonding patterns and drive phase transitions leading to the creation of new high-pressure phases with exotic properties that are inaccessible at ambient pressure. Using the swarm intelligence structural prediction method, the phase transition of TiF_(3), from R-3c to the Pnma phase, was predicted at high pressure, accompanied by the destruction of TiF_6 octahedra and formation of TiF_8 square antiprismatic units. The Pnma phase of TiF_(3), formed using the laser-heated diamond-anvil-cell technique was confirmed via high-pressure x-ray diffraction experiments. Furthermore, the in situ electrical measurements indicate that the newly found Pnma phase has a semiconducting character, which is also consistent with the electronic band structure calculations. Finally, it was shown that this pressure-induced phase transition is a general phenomenon in ScF_(3), VF_(3), CrF_(3), and MnF_(3), offering valuable insights into the high-pressure phases of transition metal trifluorides.

Progress in functional studies of transition metal borides

In recent years,transition metal borides(TMBs)have attracted much attention because they are considered as potential superhard materials and have more abundant crystal structures compared with traditional superhard materials.So far,however,no superhard materials have been found in TMBs.A large number of structures and potential new properties in TMBs are induced by the various hybridization ways of boron atoms and the high valence electrons of transition metals,which provide many possibilities for its application.And most TMBs have layered structures,which make TMBs have the potential to be a two-dimensional(2D)material.The 2D materials have novel properties,but the research on 2D TMBs is still nearly blank.In this paper,the research progress of TMBs is summarized involving structure,mechanical properties,and multifunctional properties.The strong covalent bonds of boron atoms in TMBs can form one-dimensional,twodimensional,and three-dimensional substructures,and the multiple electron transfer between transition metal and boron leads to a variety of chemical bonds in TMBs,which are the keys to obtain high hardness and multifunctional properties of TMBs.Further research on the multifunctional properties of TMBs,such as superconductors,catalysts,and high hardness ferromagnetic materials,is of great significance to the discovery of new multifunctional hard materials.

Synthesis and Crystal Structure of (CO) 5ReSnMe 2Re(CO) 5

The crystal structure of the title complex (CO) 5ReSnMe 2Re(CO) 5, (C 12 H 6O 10 Re 2Sn, M r =801.27), has been determined by single crystal X ray diffraction. The crystal is monoclinic with space group P2 1/n (NO.14), a=10.587(2), b=12.392(2), c = 14.594(3) , β = 100.59(3)°, V = 1882(1) 3, D x = 2.828 g·cm -3 , F(000)=1432, μ =14.3759mm -1 , Z =4, and final R =0 0440 and R w =0 0483 for 1954 reflections ( I≥3σ(I )). In the complex the Sn atom is connected to two methyl groups and two Re atoms which are in slightly distorted tetrahedral arrangement. The Re atom is coordinated by five carbonyl ligands and one Sn atom, forming an octahedral structure.

Solvothermal Synthesis and Crystal Structure of Zn(en)_3B_5O_7(OH)_3

A new polyborate containing ehiral metal-complex Zn（en）3 B5O7（OH）3, where en = ethylenediamine, was synthesizedunder solvothermal conditions and structurally characterized by means of X-ray diffraction analysis. Crystal data： Zn（en）3 B5O7（OH）3, monoclinic, space group P21/c, a =0.8532（72） nm, b =2.3340（5） nm, c = 0.9526（92） nm, β =107. 04（3）°, Z=4, V=1.8140（6） nm^3, Dc =1.694 g/cm^3, p=1.416 mm^-1, F（000） = 960, GOF = 1. 020, R =0. 0276, Rw =0. 0828. There is a chiral Zn（en）3^2＋ complex cation and an isolated B5O7（OH）3^2- group in a Zn（en）3 B5O7（OH）3 molecule. The enantiomer of the chiral complex cation is separated orderly as ,4 and A configurations in the compound and the borate group consists of two B303 cycles linked through a bridging boron atom.

A New Heterometallic 3d-3d Transition Metal Oxo-cluster{Cu^(Ⅱ)_(6)Mn^(Ⅲ)}:Synthesis,Crystal Structure and Magnetic Property

A new transition metal-antimony oxo-cluster based compound has been synthesized in water under room temperature.Its formula is Na_(6)[Cu_(6)MnSb_(6)(μ_(3)-OH)_(2)(OH)(μ_(4)-O)_(6)(tartrate)_(6)]-_(2)0H_(2)O(1),where tartrate represents rac-tartaric acid.It was characterized by elemental analysis,infrared spectrum and X-ray single-crystal diffraction.The compound crystallizes in the monoclinic system,space group P2_(1/n).Structural analyses revealed that two Sb_(3)(μ_(3)-0)(tartrate)_(3)scaffolds sandwich a Cu^(Ⅱ)_(_(6))Mn^(Ⅲ)middle layer to form the cluster.In the middle layer,all the seven metal ions lie in an almost regular hexagon,with Mn^(Ⅲ)ion in the center and six Cu^(Ⅱ)ions along the edges of the hexagon.As a 4-connected node,each cluster is interlinked to its nearest four{Cu_(6)Mn}neighbors through Na^(+),generating a 3D supramolecular framework.The temperature-dependent magnetic susceptibilities indicated dominating antiferromagnetic interactions in 1 with J_(Cu-Cu)=176.34 and J(Cu-Mn)=-14.44 cm^(-1).

METAL CLUSTERS SYNTHESIZED BY SOLID STATE REACTION——PREPARATION AND CRYSTAL STRUCTURE OF TWO MIXED METAL CLUSTERS,Ni_2Nb_2Te_4(Ⅰ) AND Ni_2Ta-2Te_4(Ⅱ)

The two title compounds obtained by solid state reaction at high temperature were char-acierized as isomorphism by single--crystal X--ray diffraction. The space group of both crys-tals is C_(2v)~4-Pma2, with lattice constants a = 7.955(1), b=6.258 (1), c=7 .203(2)A forI, and a =7.914 (1), b=6.237 (1), c=7.236 (1) ? for Ⅱ, Z=2. The structures were de-termined by normal method and refined to the final R = 0.074 and 0.083, respectively. Theresults show that the structure may be regarded as building by cluster unit with formulaNi_2M_2Te_4 (M =Nb or Ta) in which two Ni atoms and two M atoms form a rhombus, whilethe Te atoms are distorted tetrahedrally coordinated with both kinds of metal atoms. In thecluster unit there exist interactions between Ni atoms as well as between Ni and M atoms.In addition, all the cluster units are linked together not only by bridging Te atoms, but alsoby weaker metal-metal interactions, so as to form two--dimensional network. Therefore, thestructure may be represented by the formula [Ni_2M_2(μ_4--Te)_(6/3) (μ_4--Te)_(4/2) ]_∞. A preliminarymeasurement of electric conductivity shows that the crystals of the two title compounds aremetallic but their conductivities are anisotropic; those parallel to the a-b axes are about10~3Ω^(-1)·cm^(-1), whereas those along the c axis are about 10Ω^(-1)·cm^(-1).

Pressure-induced phase transition and electronic structure evolution in layered semimetal HfTe_(2)

Motivated by the recent experimental work,the pressure-induced structural transition of well-known two-dimensional(2D)1T-Hf Te_(2)was investigated up to 50 GPa through the advanced CALYPSO structure search technique combined with the first-principles calculations.Our calculations suggested that the 1T-Hf Te_(2)will first transform to C2/m phase at 3.6 GPa with a volume reduction of 7.6%and then to P62m phase at 9.6 GPa with a volume collapse of 4.6%.The occurrences of 3D C2/m and P62m phases mainly originated from the enhanced Te-Te interlayer coupling and the drastic distortions of Hf-Te polyhedrons in P3m1 phase under compression.Concomitantly,the coordination number of Hf atoms increased from six in P3m1 to eight in C2/m and eventually to nine in P62m at elevated pressure.The metallic and semimetallic nature of C2/m and P62m phases were characterized,and the evidence of the reinforced covalent interactions of Te-Hf and Te-Te orbitals in these two novel high-pressure phases were manifested by the atom-projected electronic DOS and Bader charge.

Syntheses,Crystal Structures and Fluorescence Properties of Two Complexes Based on a New Chiral Ligand

A new homochiral ligand,（R）-2-（4-pyridyl）-4,5-dihydrothiazole-4-carboxylic acid（HL^R）, has been synthesized. Two complexes, [ZnL2^R（H2O）2]·H2O（1） and [MnL2^R（H2O）2]？H2O（2） have been prepared by the reactions of Zn（Ⅱ） and Mn（Ⅱ） ions with the ligand HLR, and characterized by single-crystal X-ray diffraction analysis and fluorescence. Complexes 1 and 2 are isomorphs, and both of the Zn（Ⅱ） and Mn（Ⅱ） centers in 1 and 2 are six-coordinated by the two NO units of two ligands and two water oxygen atoms, showing distorted octahedral coordination geometry. Complexes 1 and 2 show fluorescent properties in the solid state at room temperature.

Local electronic structure and magnetic properties of 3d transition metal doped GaAs

The local electronic structure and magnetic properties of GaAs doped with 3d transition metal (Sc, Ti, V, Cr, Mn, Fe, Co, Ni) were studied by using discrete variational method (DVM) based on density functional theory. The calculated result indicated that the magnetic moment of transition metal increases first and then decreases, and reaches the maximum value when Mn is doped into GaAs. In the case of Mn concentration of 1.4%, the magnetic moment of Mn is in good agreement with the experimental result. The coupling between impure atoms in the system with two impure atoms was found to have obvious variation. For different transition metal, the coupling between the impure atom and the nearest neighbor As also has different variation.

Synthesis and crystal structure of trinuclear Fecarbonyl cluster Fe_3(CO)_8S_2CNC_6H_5

Metal cluster chemistry is an active studying field nowadays. It is possible that metal clusters can be developed as new homogeneous catalysts with special functions. Organoiron clusters, which could be easily synthesized at lower price, are very important in metal cluster chemistry. Fe3（CO）12 is a very useful compound with higher activity than Fe（CO）5 in

Synthesis and Structure of Propionate－bridged Mixed－metal Cluster Compound：〔MoW2O2（O2CC2H5）6（H2O）3〕ZnBr4·4H2O

The heterotrinuclear cluster compound [MoW2O2 （O2CC2H5 ）6-（ H2O）3] ZnBr4·4H2O was prepared by the redox reaction of Mo （CO）6 with Na2WO4 in propionic anhydride. The crystal is monoclinic of space group P2/c with a =16. 334（4） , b= 9. 657（5） , c=19. 889（9） ,β= 139. 79 （5）°,V= 2026 （2） ￣3 , Z=2 , Dc=2. 30 g/cm￣3 μ（MoKa） =106. 6 cm￣（-1） ,F（000）=1176 ,final R=0. 065 and Rω=0. 072 for 1964 reflections with I≥3σ（I）. In the structure of cation [MoW2O2 （O2CC2H5 ）6 （H2O）3]￣（2+） molybdenum and tungsten atoms are statistically disordered. Three metal atoms form an equilateral triangle with the distance of M-M being 2. 735.

A novel superhard tungsten nitride predicted by machine-learning accelerated crystal structure search

Transition metal nitrides have been suggested to have both high hardness and good thermal stability with large potential application value, but so far stable superhard transition metal nitrides have not been synthesized. Here, with our newly developed machine-learning accelerated crystal structure searching method, we designed a superhard tungsten nitride, h-WN6, which can be synthesized at pressure around 65 GPa and quenchable to ambient pressure. This h-WN6 is constructed with single-bonded armchair-like N6 rings and presents ionic-like features, which can be formulated as W^2.4＋N^2.4-. It has a band gap of 1.6 eV at 0GPa and exhibits an abnormal gap broadening behavior under pressure. Excitingly, this h-WN6 is found to be the hardest among transition metal nitrides known so far （Vickers hardness around 57 GPa） and also has a very high melting temperature （around 1,900 K）. Additionally, the good gravimet- ric （3.1 kJ/g/and volumetric （28.0 kJ/cm3） energy densities make this nitrogen-rich compound a potential high-energy-density material, These predictions support the designing rules and may stimulate future experiments to synthesize superhard and high-energy-density material.