SYNTHESIS AND CHARACTERIZATION OF THE SOLID COMPLEXES OF Mn(Ⅱ), Co(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Ag(Ⅰ), Cd(Ⅱ) NITRATES WITH DISUBSTITUTED BENZO CROWN ETHERS

Nine new solid complexes of Mn(Ⅱ),Co(Ⅱ),Cu(Ⅱ),Zn(Ⅱ.),Ag(Ⅰ) nitrates with 4',5'-dibromobenzo-15—crown—5(L_A),Ag(Ⅰ),Cd(Ⅱ)nitrates with tetrabromodibenzo—18—crown—6(L_B)and Cu(Ⅱ), Ag(Ⅰ) nitrates with 4'—bromo—5'—nitrobenzo—15—crown-5(L_c),having the compositions of M(NO_2)_2·L·nH_2O(M=Mn,Co, Zn,L=L_A,n=2;M=Cu,L=L_A,n=1.5; M=Cd, L=L_B,n=0; M=Cu,L=Lc,n=2) and AgNO_·L·nCH_3CN(L=LA,n=0; L=L_B,n=1; L=Lc,n=1/2) have been synthesized in nonaqueous solvent. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X—ray powder diffraction analysis, molar conductance and measuremends of solubility in some general solvents.     

Two Novel {Ti_6P_2} Clusters Decorated with Inorganic Acids

Two inorganic acids decorating titanium-oxo clusters (PTCs),Ti_6O_4(O~iPr)₁₀(O₃P-Phen)₂(NO₃)₂(PTC-251) and Ti_6O_4(O~iPr)₁₀(O₃P-Phen)₂(HSO_4)₂ (PTC-252)(H₂O₃P-Phen=phenylphosphinic acid) have been synthesized under solvothermal conditions.As a result of the labile coordination sites of the{Ti_6P₂}unit,nitrite and sulfate adopt different capping mode.Besides,they also present different space packing.The photocatalytic H₂evolution activities of these obtained PTCs have been studied,with sulfate decorating PTC-252 presenting a maximum H₂ production rate up to 110.95μmol·g^-1·h^-1.     

Synthesis,Crystal Structure and Antitumor Activity of a Ca(Ⅱ) Coordination Polymer Based on 4-Acetylphenoxyacetate Ligands

A novel Ca(Ⅱ) coordination polymer,[Ca L₂(H₂O)₂]_n (1,HL=4-acetylphenoxyacetic acid) has been synthesized with 4-acetylphenoxyacetic acid,Ca(ClO_4)₂·4H₂O and Na OH as raw materials.Complex 1 was characterized by elemental analysis and single-crystal X-ray diffraction analysis.The results show that the Ca(Ⅱ)ion is eight-coordinated in a distorted triangular dodecahedral geometric configuration with six carboxylate Oatoms of four L ligands and two O atoms of two coordinated water molecules.Complex 1 forms a one-dimensional chained structure by the bridging effect of carboxylate O atoms.The antitumor activity of HLligand and complex 1 has also been investigated.     

Hydrothermal Synthesis,Crystal Structure and Properties of a New Binuclear Nickel(Ⅲ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

A new binuclear nickel(II) complex Ni₂(HPT)_4(H₂O)₃ (1) has been hydrothermally synthesized with nickel hydroxide,3,4-pyridine dicarboxylic acid and 3-(pyridin-2-yl)-1,2,4-triazole (HPT) in the mixed solution (the volume ratio of methanol and water is 1:4).It crystallizes in tetragonal space group P4₂/n,with a=20.844(1),b=20.844(1),c=7.2463(7)A,V=3148.2(5)A³,D_c=1.587 g/cm³,Z=4,μ(Mo Ka)=1.257,F(000)=1544,the final GOOF=1.043,R=0.0437 and w R=0.1297.The crystal structure shows that the whole molecule consists of two nickel ions which are bridged by fourμ₂-η¹:η^0-3-(pyridin-2-yl)-1,2,4-triazole anions.The coordination environment of Ni(II) ion is Ni N₆,giving a distorted octahedral geometry.The thermal stability and fluorescent and magnetic properties of the complex were investigated.     

Explicating the Role of Metal Centers in Porphyrin-Based MOFs of PCN-222（M） for Electrochemical Reduction of CO2

The porphyrin-based MOFs formed by combining Zr₆ clusters and porphyrin carboxylic acids with clear M-N₄ active centers show unique advantages in electrocatalytic reduction of CO₂（CO₂RR）. However, its conductivity is still the bottleneck that limits its catalytic activity due to the electrical insulation of the Zr cluster. Therefore, the porphyrin-based MOFs of PCN-222（M）(M = Mn, Co, Ni, Zn) with explicit M-N₄ coordination were combined with...     

In-situ cation exchange enhances room temperature phosphorescence of a family of metal-organic frameworks

The rational designability and chemical tunability of metal-organic frameworks(MOFs)are enabling tributes to efficaciously enhance their room temperature phosphorescence(RTP)performance.A family of stable anionic MOFs,[Zn₂(4,5-ImDC)₂]M₂(NKU-132,M=(CH₃)₂NH₂or(CH₂CH₃)₂NH₂),featuring significant RTP have been synthesized.By rational cation selection and in-situ replacement from dimethylammonium to diethylammonium,the phosphorescence lifetime is increased from 30.88 to126.3 ms,along with less sensitivity to air.This work provides an anti-quenching and lifetime tuning example for RTP-MOFmaterials via facile host-guest chemistry.     

乙二胺三乙酸与锌(Ⅱ)、钴(Ⅱ)相互作用的固体和溶液化学特性

在水热和弱酸性反应条件下,螯合型表面活性剂前驱体乙二胺三乙酸分别与氯化锌、氯化钴反应,形成水合乙二胺三乙酸金属配合物[M(H₂O)₆][M(ED3A)(H₂O)]₂·2H₂O[M=Zn(1),Co(2);H₃ED3A=乙二胺三乙酸,C₈H₁₄N₂O₆]。 产物经元素分析、红外、热重、液体核磁共振和X射线单晶衍射结构表征。 乙二胺三乙酸和锌(Ⅱ)、钴(Ⅱ)五配位,并与水一起形成典型的[MN₂O₄]或[MO₆]八面体结构。 ¹³C核磁共振实验结果表明,溶液中乙二胺三乙酸与锌形成配合物在弱酸性条件下(pH值3~7)稳定存在,在酸性溶液中完全解离,乙二胺三乙酸进一步经分子内成环反应生成3-酮哌嗪二乙酸(H₂kpda=C₈H₁₂N₂O₅)。     

基于柔性四羧酸的三个一维/二维/三维Zn(Ⅱ)/Co(Ⅱ)配合物的晶体结构及荧光性质

通过水热/溶剂热合成的方法制备了3个Zn(Ⅱ)/Co(Ⅱ)配合物{[Zn(H₂L)(H₂O)₃]·H₂O·0.5H₄L}_n(1)、{[Co(L)_0.5(4,4'-bpy)]·0.5H₂O}_n(2)和{[Co(L)_0.5(pbmb)(H₂O)]·H₂O}_n(3)(H₄L=5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid,4,4'-bpy=4,4'-bipyridine,pbmb=1,1'-(1,3-propane)bis-(2-methylbenzimidazole))。结构分析表明配合物1为一维链结构。2为拓扑符号为(6⁴·7·8)(6·7²)的三重穿插网络结构。3是拓扑符号为(4·6²)(4²·6²·8²)的(3,4)-连接的二维网络结构。配合物1呈现出较好的荧光性质。     

A quadruple helicene with a rubicene core: synthesis,structural analyses and properties

We report the synthesis of a quadruple helicene with a rubicene core R1 by a Scholl reaction.Among the 10 stereoisomers including 4 pairs of enantiomers and 2 meso isomers,only 2 pairs of enantiomers and 1 meso isomer have been isolated.The sample structures were unambiguously determined by X-ray crystallography to be(P,P)₆-(P,P)₅/(M,M)₆-(M,M)₅-R1-A,which has a propeller-shaped structure,and(M,M)₆-(P,P)₅/(P,P)₆-(M,M)₅-R1-B and(M,P)₆-(P,M)₅-R1-C,which have saddle-shaped structures.The chiral resolutions of R1 were carried out by chiral HPLC,revealing two pairs of chiral stereoisomers(P,P)₆-(P,P)₅/(P,P)₆-(M,M)₅,(M,M)₆-(P,P)₅/(M,M)₆-(M,M)₅ as well as a meso isomer(M,P)₆-(P,M)₅,which were further characterized by CD spectroscopy and time-dependent density functional theory(TD-DFT)calculations.Surprisingly,the UV-vis absorption and emission spectra of these resolved stereoisomers and unresolved R1 were almost identical.In addition,the chemical oxidation of R1 led to the formation of radical cations and dications at room temperature.     

Investigating the Effects of Para-methoxy Substitution in Sterically Enhanced Unsymmetrical Bis(arylimino)pyridine-cobalt Ethylene Polymerization Catalysts

A group of five bis(arylimino)pyridine-cobalt(Ⅱ)chloride complexes,[2-{(2,6-(Ph₂CH)₂-4-MeOC₆H₂)N=CMe}-6-(ArN=CMe)C_5 H₃N]CoCl₂(Ar=2,6-Me₂C₆H₃Co1,2,6-Et₂C₆H₃Co2,2,6-iPr₂C₆H₃Co3,2,4,6-Me₃C₆H₂Co4,2,6-Et₂-4-MeC₆H₂Co5),each containing one N-4-methoxy-2,6-dibenzhydrylphenyl group and one smaller sterically/electronically variable N-aryl group,have been synthesized in good yield(>71%)from the corresponding neutral terdentate nitrogen-donor precursor,L1-L5.All complexes have been characterized by¹H-NMR and FTIR spectroscopy with the former highlighting the paramagnetic nature of these cobaltous species and the unsymmetrical nature of the chelating ligand.The molecular structures of Co3 and Co4 emphasize the steric differences of the two inequivalent N-aryl groups and the distorted square pyramidal geometry about the metal centers.In the presence of MAO or MMAO,Co1-Co5 collectively displayed high activities for ethylene polymerization producing high molecular weight polyethylenes that,in general,exhibited narrow dispersities(M_w/M_n values:2.12-4.07).Notably,the least sterically hindered Co1 when activated with MAO was the most productive(6.92×10⁶g_PE·mol^-1_(Co)·h^-1)at an operating temperature of60℃.Conversely,the most sterically hindered Co3/MMAO produced the highest molecular weight polyethylene(M_w=6.29×10⁵g·mol^-1).All the polymers displayed high linearity as demonstrated by their melting temperatures(>130℃)and their~1 H-and¹³C-NMR spectra.By comparison of Co1 with its para-methyl,-chloro and-nitro counterparts,the presence of the para-methoxy substituent showed the most noticeable effect of enhancing the thermal stability of the catalyst.     

Two New Copper Complexes by H_4AQTC(Anthraquinone-1,4,5,8-tetracarboxylic Acid):Syntheses,Structures and Properties

Two new complexes[Cu(AQTC)_0.5(H₂O)₃]·3H₂O}_n (1,H₄AQTC=anthraquinone-1,4,5,8-tetracarboxylic acid) and Cu[(Py)₂C(OH)₂]₂(H₂AQTC)·2H₂O (2,(Py)₂CO=di-2-pyridyl ketone) have been prepared and characterized by elemental analyses and IR spectroscopy.X-ray crystallographic studies show that complex 1crystallizes in monoclinic space group C2/m and complex 2 in monoclinic space group P2_1/c.Complex 1 features a1D chain structure by carboxyl oxygen atoms.Complex 2 displays a mononuclear structure and anions and cations are separated.What's interesting is that the ligand of H₄AQTC with eight carboxyl oxygen atoms and two quinone oxygen atoms does not directly coordinate with metals,and only exist as a counter-anion in complex 2.Three-dimensional structures of two complexes are formed by intermolecular interactions.The thermogravimetric analyses of two complexes are investigated.The luminescent properties of complex 1 are investigated as well.     

Noncentrosymmetric K2Mn3(SO4)3F2·4H2O and Rb2Mn3(SO4)3F2·2H2O with pseudo-KTP structures

Two fluoride sulfates,K₂Mn₃(SO₄)₃F₂·4H₂O(Ⅰ) and Rb₂Mn₃(SO₄)₃F₂·2H₂O (Ⅱ) are obtained by water solution method.Single-crystal X-ray diffraction analysis indicated that they crystallize in space groups of Cmc2_1.Their structures feature a pseudo-KTP structure consisting of interconnecting[Mn₃(SO₄)3F₂(H₂O)2]_∞ layers,which are further packing along the a axis with alkali metal cations balancing the charges.The structure relationships between the two compounds are discussed.Secondharmonic generation measurements manifest that Ⅰ and Ⅱ have similar second-harmonic generation responses of about 0.2 and 0.25 times that of KH₂PO₄.     

Synthesis,Crystal Structure and Fluorescence Property of a Zinc(Ⅱ) Coordination Polymer with a Theoretical Calculatio

We have designed and synthesized a new luminescent coordination polymer[Zn₂(NO₃)(NCP)₃(H2O)₃]n·2 nH₂O(1,HNCP=2-(2-carboxyphenyl)imidazo-[4,5-f]-1,10-phenanthroline)under hydrothermal conditions,which has been structurally characterized by single-crystal X-ray diffraction analyses.1 crystallizes in monoclinic,space group P2₁/n,with a=13.7748(3),b=19.2651(4),c=19.9543(4)?,β=95.339(2)o,V=5272.35(19)?³,C₆₀ H_39.73 N₁₃ O_13.33 Zn₂,M_r=1286.80,D_c=1.621 g/cm³,Z=4,μ(Mo Ka)=2.118,F(000)=2629,the final R=0.0598 and w R=0.1483.In 1,the organic ligand NCP-displays two different bridging modes to connect adjacent Zn(II)ions into a 1 D chain along the c-direction.Photoluminescent analyses reveal that 1 exhibits a strong green emission with a fluorescent lifetime of 5.57 ns.The first-principle calculation results show that the luminescence mainly originates from ligand-centered charge transition.     

Catalytic conjugate addition of indole toα,β-unsaturated ketones by Co（ClO4）-2·6H2O/bis-Schiff base complexes

Co（ClO₄）)₂·6H₂O/bis-Schiff base complexes promoted the conjugate addition of indole toα,β-unsaturated ketones under mild conditions,giving the corresponding addition products with high yields.And the complex has been characterized with XRD and IR.     

Two Polynuclear Fe Complexes with Boat-like Core:Syntheses,Structures and Magnetic Properties

Two novel polynuclear complexes{NaFe4（μ₄-O）(L)4（μ₂-Cl）[Fe（CN）₅NO]（H₂O）(DMF)2}（1） and{NaFe4（μ₄-O）(L)4（μ₂-OEt）[Fe（CN）₅NO]（H₂O）(DMF)₂}（2） have been prepared using the tetradentate N-（2-hydroxyethyl）-3-methoxysalicylaldimine Schiff-base ligand （H₂L） with the help of[Fe（CN）₅NO]^2-linkers,where the ligand was in situ synthesized through the condensation of o-vanillin and e...     

Tetrabutylammonium salts of tritransition-metal-substituted A-α-tungstogermanate:Halogen-free and single-component catalysts for the coupling reaction of carbon dioxide and epichlorohydrin

The green synthesis of chloropropylene carbonate via the coupling reaction of carbon dioxide and epichlorohydrin had been achieved using halogen-free and single-component catalysts tetrabutylammonium salts of tritransition-metal-substituted A-α-tungstogermanate [（n-C₄H₉）₄N]₃H₇GeW₉M₃（H₂O）₃O₃₇（M = Cu^Ⅱ,Ni^Ⅱ,Co^Ⅱand Mn^Ⅱ） without any solvent.The catalytic activity was significantly depended on the transition metal introduced in polyoxometalates.[（n-C₄H₉）₄N]₃H₇GeW₉Mn₃（H₂O）₃O₃₇ exhibited the highest catalytic activity with 94.9%conversion for epichlorohydrin and 98%selectivity for chloropropylene carbonate in 3 h.Plausible mechanism was proposed based on the results.     

Syntheses,Crystal Structures and Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Complexes Based on 1,10-Phenanthroline Derivative

Two new coordination complexes[Mn(L)₂(DNSA)](1) and[Co(L)(1,4-bdc)]_n (2) have been achieved under hydrothermal conditions (H₂DNSA=3,5-dinitro-salicylic acid,1,4-bdc=1,4-benzenedicarboxylic acid and L=2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline).1 crystallizes in monoclinic,space group P2_1/c with a=15.871(3),b=17.274(4),c=16.078(3)A,β=113.03(3)^o,V=4056.6(16)A³,Z=4,C₄₅H₂₂Cl₂F₂Mn N₁₀O₇,M_r=978.57,D_c=1.602 g/cm³,F(000)=1980,μ(Mo Ka)=0.536 mm^–1,R=0.0437 and w R=0.1065.2 belongs to the monoclinic system,space group C2/c with a=14.665(2),b=30.856(4),c=11.237(2)A,β=111.166(2)^o,V=4742.0(12)A³,Z=8,C₂₇H₁₄Cl Co FN₄O₄,M_r=517.80,D_c=1.602 g/cm³,F(000)=2312,μ(Mo Ka)=0.889 mm^–1,R=0.0364 and w R=0.0862.The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion.In 2,the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure.The luminescence of 1 has been studied in detail.Moreover,thermal behaviors of 1 and 2 are also investigated.     

Luminescent Lanthanide-titanium-organic Compound Constructed by Tetra-nuclear Ln-Ti Building Units and Diphenylglycolic Acid

(Under solvothermal conditions with the mixed solvents of C₂H₅OH and H₂O,a new heterometallic lanthanide-titanium-organic compound,[TbTi(μ3-O)(L₃)(H₂O)₄]·H₃O(1,H₂L=diphenylglycolic acid),has been synthesized.Compound 1 exhibits a 3D supramolecular framework by incorporating the tetra-nuclear[Tb₂Ti₂(μ3-O)2]unit and L^2-ligand.Compound 1 shows intense green luminescence.Furthermore,the PXRD,TGA and IR spectra were also studied.)     

两种具有氢键网络的Ni(Ⅱ)-咪唑配合物的晶体结构和磁性

合成了两种配合物晶体[Ni(im)₆](NO₃)(OH)(H₂O)₄(Ⅰ)和[Ni(im)₄(H₂O)₂][C₆H₄(COO)₂](Ⅱ)(im=C₃H₄N₂).晶体结构测定表明,晶体(Ⅰ)属于六方晶系,空间群P6₃/m,a=0.8985(10)nm,c=2.1002(4)nm,V=1.4685(4)nm₃,Z=2,R=0.043,R_w=0.045.晶体(Ⅱ)属单斜晶系,空间群C2/c,a=2.2207(4)nm,b=0.7665(2)nm,c=1.6043(3)nm,β=120.60(3)°,V=2.3503(9)nm₃,Z=4,R=0.056,R_w=0.079.两种配合物在结构上的突出特点是通过氢键形成了三维无限伸展的氢键电荷传递体系,对分子间电子传递有调节和促进作用,从而对晶体的磁性质产生了一定影响。     

A Novel 3D CdⅡ-CP Based on a Bi-functional（N-/O-Sites） Triazole-modified Carboxyl Ligand: Structure,Topology and Photoluminescence

With triazole-modified derivative as link,one new framework[Cd₅(μ₅-HL^2-)₂(μ₄-L^3-)₂（H₂O）₁₀]·2H₂O(1,H₃L=2-（1,2,4-triazol-1-yl）benzene-1,3,5-tricarboxylic acid) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,powder X-ray diffraction and elemental analysis.Complex 1exhibits a 3D （3,4,6）-connected net cross-linked by binuclear[Cd₂