Synthesis,Crystal Structure and Photoluminescence of a Dinulear Copper Complex

A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal structure analysis.It crystallizes in triclinic space group P2_1/n with a = 10.7520（3）,b = 18.1860（5）,c = 11.8487（3） ？,β = 91.864（2）,V = 2315.61（11） ？~3,Z = 4,Mr = 594.87,Dc = 1.706 g/cm^3,F（000） = 1176.0,μ = 12.582 mm（-1）,GOOF = 1.048,the final R = 0.0289 and wR = 0.0670 for 3787 observed reflections with I 〉 2σ（I）.The Cu atoms in the complex are four-coordinated and adopt distorted tetrahedral coordination geometry.In the solid state,the complex exhibits greenish yellow photoluminescence with a peak maximum of 533 nm,a decay time of 34 μs,and a photoluminescence quantum yield of 63.6% at room temperature,respectively.

Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

Synthesis and Crystal Structure of △~6－4－Amino－5，6－diphenyl－5－hydroxy－1，2，4－triaza－cyclohexene－3－thione－monohydrate

The title compound C（15）H（14）N4OS·H2O crystallizes in the monoclinic system, space group P21/a, with a=8. 733（3） , b= 16. 731 （4） , c=10. 476（4） A,β= 95. 41（3） °, V = 1523. 7（8） A￣3, Dc=1. 38 g/cm￣3, Z = 4,Mr= 316. 38,λ（MoKα） = 0. 71069 A, F（000） = 664,μ= 2.14 cm-1, T= 296K. Final R=0. 054,and Rω=0.063 for 1279 reflections with I≥3σ（I）. The parent structure of the molecule is a distorted six-membered ring. The effect of the steric hindrance between the two phenyls on the conjugate interactions in the heterocyclic ring has been discussed.

A Stable Polyoxometalate-based Coordination Polymer for Light Driven Degradation of Organic Dye Pollutant

A new POM-based coordination polymer,[Cl_(2)Cu^(Ⅰ)_(11)(trz)_(8)][H_(3)SiW_(12)O_(40)](1),was successfully obtained under hydrothermal reaction.The compound was characterized by single-crystal X-ray diffraction,TGanalyses,IR spectra and PXRD analysis.Compound 1 shows extreme stability and outstanding catalytic activity to the degradation of organic dye pollutant.

Synthesis,Crystal Structure and Photoluminescence of a TADF Dinuclear Cu(Ⅰ)Complex

A binuclear Cu(Ⅰ)complex[Cu(PCNP)(mepypz)]_(2)(BF_(4))_(2)(1,PCNP=2,6-bis(diphenylphosphine)-benzonitrile,mepypz=2-methyl-6-(1H-pyrazol-3-yl)-pyridine was synthesized from the reaction of Cu(CH_(3)CN)_(4)BF_(4),PCNP and mepypz in CH_(2)Cl_(2)at room temperature.The compound was characterized by NMR,UV-vis and X-ray single-crystal structure analysis.It crystallizes in monoclinic space group P2_(1/c)with a=14.0139(5),b=11.8149(3),c=27.1248(10)A,β=96.686(4)°,V=4460.6(3)A^(3),Z=2,M_(r)=1561.97,D_(c)=1.163 g/cm^(3),F(000)=1600.0,μ=1.774 mm^(–1),GOOF=1.071,the final R=0.0523 and_(w)R=0.1412 for 7919 observed reflections with I>2σ(I).The Cu atoms in the complex are four-coordinated and adopt a distorted tetrahedral coordination geometry.In the solid state,the complex exhibits yellowish-green emission with a peak wavelength of 546 nm,a lifetime of 390μs,and a quantum yield of 0.45 at room temperature.The temperature-dependent investigation of luminescent properties suggests that the complex emits thermally activated delayed fluorescence(TADF)at room temperature.

A Tetranuclear Cuprous Halide Cluster Exhibiting Efficient Blue Thermally Activated Delayed Fluorescence

A new tetranuclear cuprous halide complex,(CuBr)_(4)(PN)_(2)(PN=2-(diphenylphosphaneyl)-6-methoxypyridine),was synthesized and fully characterized.In solid state,this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3%and a decay time of 19μs at room temperature.The theoretical calculations,combined with the temperature dependence of spectroscopic properties and emission decay behaviors,indicate that the emission in the solid state originates from the ^(1,3)(MLCT+XLCT)excited states,which are in thermal equilibrium with a small energy gap of about 0.1 eV.

A Terbium(Ⅲ)-organic Coordination Polymer:Synthesis,Characterization and Its Luminescence

A new 3D terbium(Ⅲ)metal-organic network[Tb(HIMDC)(HCOO)(H_(2)O)]_(n)(complex 1)has been synthesized by Tb^(3+)ions coordinated with 4,5-imidazole dicarboxylic acid(H_(3)IMDC)and formic acid under solvothermal conditions with the mixed solvents of N,N-dimethylformamide(DMF)and H_(2)O.The unambiguous structural determination has been confirmed by single-crystal X-ray diffraction combined with elemental analysis,infrared(IR)spectrum,thermogravimetric analysis(TGA)and powder X-ray diffraction(PXRD).Complex 1crystallizes in orthorhombic Fdd2 space group with a=22.295(2),b=24.097(3),c=6.7256(6)?,V=3613.3?^(3),Z=16,D_(c)=2.765 g/cm^(3),F(000)=2816,μ=7.855 mm^(-1),the final R=0.0173(I≥2σ(I)),w R=0.0416(all data)and GOOF=1.068.In complex 1,the Tb^(3+)ions are connected by HIMDC^(2-)anions into 2D metal-organic layers which are further extended into a three-dimensional(3D)architecture through formic acid functional motif.In addition,complex 1 shows intense and characteristic green luminescence.

Bio-inspired Materials for Photocatalytic Hydrogen Production

After millions of years of evolution,species in nature have structures and complex elements that are difficult to synthesize artificially.Moreover,these fine structures and compositions are often beneficial to improve the photocatalytic performance.Therefore,various materials with special morphology,pore structure and element composition derived from biomass have emerged and are widely used.This mini review focuses on the preparation of bio-inspired materials and their current status in photocatalytic hydrogen production.Hopefully,this will bring new perspectives to researchers and make them learn more about the advantages of"learning from nature"and pay more attention to the green design of material structures.

First Isolation and Confirmation of Sterol Based on β-sitosterol Skeleton from the Leaves of Podocarpusnagi Planted in Fujian, Preliminary in vitro Anticancer Activity and the Crystal Structure

The crystal of(24 R)-3β,5α-dihydroxy-24-ethyl-5α-cholestan-6-one(1) was isolated from the leaves of P.nagi planted in Fujian for the first time with the same skeleton as 26,27-dinorcholest-5-en-3-β-ol(2) andβ-sitosterol(3) that have been reported before.Compound 1 crystallizes in monoclinic,space group P2_(1) with a=10.8482(4),b=7.3671(3),c=33.7860(15) A,β=93.103(4)°,V=2696.21(19) A^(3),Z=75,M_(r)=446.70,ρ_(calc)=1.145 g/cm^(3),F(000)=1032,μ=0.572 mm^(-1),GOOF=1.034,the final R=0.0467 and wR=0.1129 for 6989 observed reflections with I> 2σ(Ⅰ).Compound 2 was selected to evaluate for their preliminary in vitro anticancer activity against four cancer cell lines for the first time.The results showed that compound 2 exhibited great inhibition against gastric cancer,breast cancer MCF-7,lung cancer A549 and Helacell lines with the inhibitions of89.16% ± 1.17,97.02%±0.53,47.20%±2.58 and 36.89%±1.22 respectively at the concentration of 1.4×10^(-2) M,which means that we found the new anticancer compound in this plant medicine.

Self-organized TiO_(2)Nanotube Arrays with Controllable Geometric Parameters for Highly Efficient PEC Water Splitting

In this report,a series of self-organized TiO_(2)nanotube arrays were prepared by anodization of titanium foil in mixed electrolytes composed of water,ethylene glycol,and NH_(4)F.Their photoelectrochemical(PEC)performance as a photoanode was characterized by the PEC water-splitting hydrogen(H_(2))generation reaction.The internal relationship between the TiO_(2)nanotube arrays(TNTAs)morphology and their PECperformance was thoroughly investigated.Our results show that when the etching time is 10 hours,the length of the as-prepared TNTAs is about 20.78μm and the measured photocurrent density is around 1.25 m A·cm^(-2)with applied bias voltage 0.6 V(vs.Ag/Ag Cl)under simulated sunlight irradiation,which is 976 times higher than that of the TiO_(2)substrate without nanotubes architecture(0.00128 m A×cm^(-2)).More interestingly,the results of the IPCEmeasurement show that the band-gap of the as-prepared TNTAs is reduced from 3.20 to 2.83 eV.The corresponding optical response limit is also extended from 400 nm to TiO_(2)nanotube arrays is 510 nm,which indicates that the increasement of the TNTAs PEC performance benefits from the great improvement of its utilization of both the UVand visible light irradiation.

Two Polyoxometalate-based Host-guest Compounds:Synthesis,Crystal Structure and Catalytic Performance

Two polyoxometalate-based host-guest compounds,(HL1)2(HPW12O40)〜11H2O(1),(HL2)3(PWi2O40)·3H2O(2)(L_(1)=guanine,L_(2)=2-(1H-1,2,4-triazol-3-yl)pyridine),were synthesized under hydrothermal conditions and characterized by EA,PXRD,TG,FT-IR and X-ray single-crystal diffraction.Compound 1 crystallizes in trigonal space group P-3 with a=18.2917(5),b=18.2917(5),c=13.5441(5)A,V=3924.5(3)A^(3),Z=3,Mr=3383.26 g/mol,pcak=4.036 g/cm^(3),F(000)=4137,=48.532 mm^(-1),GOOF=1.062,the final R=0.0713 and wR=0.1865 for 9037 observed reflections with I>2σ(I).Compound 2 crystallizes in trigonal space group R-3 with a=19.0017(6),b=19.0017(6),c=25.6361(9)A,V=8016.2(6)A^(3),Z=6,Mr=3372.45 g/mol,p_(calc)=4.188 g/cm,F(000)=8886,μ=47.644 mm^(-1),GOOF=1.077,the final R=0.0380 and wR=0.0976 for 5904 observed reflections with I>2σ(I).These two compounds can catalyze selective oxidation of aniline with H2O2 as the oxidant.Under optimal conditions,the conversion of aniline with compound 1 can reach up to 91.25%,and the selectivity of nitrosobenzene is 78.81%.

Crystal Structure and Photophysical Property of 9-(4-(5-(6-Methylpyridin-2-yl)-3-phenyl-1H-1,2,4-triazol-1-yl)phenyl)-9H-carbazole

X-ray single-crystal structure analysis,UV-Vis,and photoluminescent properties of organic compound,9-(4-(5-(6-methylpyridin-2-yl)-3-phenyl-1H-1,2,4-triazol-1-yl)phenyl)-9H-carbazole(compound 1)were studied.Compound 1 crystallizes in monoclinic system,space group P2(1/c)with a=16.0434(9),b=17.920(1),c=8.3453(5)A,β=94.142(5)°,V=2393.0(2),Z=4,Mr=477.55,Dc=1.326 g/cm^3,F(000)=1000,μ=0.080 mm^–1,GOOF=1.025,the final R=0.0505 and wR=0.1226 for 4921 observed reflections with I>2σ(I).Compound 1 is a donor-acceptor type molecule,in which the carbazolyl group(cz)acts as an electron donor,and the group of 2-(1,3-diphenyl-1H-1,2,4-triazol-5-yl)-6-methylpyridine(MePyTz)as an electron acceptor.In methylene chloride,compound 1 exhibits deep blue luminescence with maximum at 440 nm,lifetime of 4.2 ns under N2 and quantum yield ofф=0.18 at room temperature.The experimental and computational results show that the emission of compound 1 originates from the lowest singlet excited state(S1)with charge transfer character.