Synthesis,Crystal Structure and Photoluminescence of a Blue-emitting Dinulear Copper Complex

A binuclear cuprous complex [Cu(μ-I)(NP)]_2·CH_2Cl_2(1, NP = 1-(2-(diphenylphosphino)phenyl)-3,5-dimethylpyrazole) was synthesized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1 with a = 9.2838(6), b = 12.2672(7), c = 12.4033(7) ?, α = 114.941(6), β = 108.707(5), γ = 91.717(5)o, V = 1190.51(12) ?~3, Z = 1, M_r = 1178.58, D_c = 1.644 g/cm~3, F(000) = 582, μ = 13.232 mm~(-1), GOOF = 1.016, the final R = 0.0384 and wR = 0.1015 for 4145 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 blue photoluminescence with a peak maximum of 468 nm, a decay time of 9 μs, and a photoluminescence quantum yield of 16.8% at room temperature, respectively. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of experimental and DFT calculations suggest that the excited states in the solid state are of(M+X+L)LCT character.     

Synthesis,Crystal Structure and Photoluminescence of a TADF Cuprous Complex

A four-coordinate mononuclear cuprous complex oCBP-Cu-Pym(1, oCBP =1,2-bis(diphenylphosphine)-nido-carborane, Pym = 2-methyl-6-(1 H-pyrazol-1-yl)pyridine) was synthe-sized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group C2/c with a = 28.4182(8), b =16.2994(4), c = 22.2708(5) ?, β = 127.219(2)°, V = 8214.8(3) ?3, Z = 8, Mr = 766.92, ρcalc = 1.24 g/cm3, F(000) = 3160, μ = 2.30 mm–1, GOOF = 1.063, the final R = 0.0700 and wR = 0.1903 for7158 observed reflections with I 2σ(I). The Cu(I) ion adopts a highly distorted tetrahedral geometry defined by two nitrogen and two phosphorous atoms. Under UV 365 nm at room temperature, this complex exhibits green emission with maximum emission peak at 516 nm,lifetime 32.4 μs and quantum yield(ф = 0.461) in the solid state. Photophysical investigation suggests that the emission of complex 1 at room temperature was attributed to TADF, which is strongly supported by theoretic calculation.     

Synthesis,Crystal Structure and Photoluminescence of a TADF Cuprous Complex

A cuprous mononuclear copper complex [Cu(adpypz)CH3CNPPh3]BF4·CH2Cl2(1, adpypz = 9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)pyridin-2-yl)-9,10-dihydroacridine) was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388(4), b = 13.4569(4), c = 16.2561(6) ?, α = 97.154(3), β = 92.187(3), γ = 114.119(4)°, V = 2235.38(13) ?3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm~3, F(000) = 996, μ = 2.62 mm~(–1), GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm(1), lifetimes 235 μs and quantum yields(ф = 0.279) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.     

Hydrothermal Synthesis and Crystal Structure of a Copper Complex

The title compound [Cu(IB)2]n·n(H2O) 1 was synthesized via the hydrothermal reaction of CuSO4·5H2O and NaOH with 4-(1H-Imidazol-1-yl)benzoic acid(HIB),and character-rized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in monoclinic,space group C2/c with a = 14.349(7),b = 5.977(3),c = 21.368(9) ,β = 104.956(9)o,V = 1770.5(2)3,Z = 4,C20H16CuN4O5,Mr = 455.92,Dc = 1.710 g/cm3,F(000) = 932 and μ(MoKα) = 1.279 mm-1.The final R = 0.0337 and wR = 0.0888 for 1972 observed reflections with Ⅰ 2σ(Ⅰ) and R = 0.0369 and wR = 0.0926 for all data.X-ray diffraction reveals that the IB ligand links the Cu(Ⅱ) atoms into a double stranded chain.The extensive supramolecular interactions lead to the formation of an infinite 2D structure.     

Synthesis and Crystal Structure of a New Mononuclear Copper Complex

<正>A new kind of Cu (II) complex [Cu(tpmb)2Cl2]·CH3OH·H2O (tpmb = 1,3,5-tri(2-pyrimidinyl)sulfanylmethyl-2,4,6-trimethylbenzene) was synthesized, and its structure has been determined by X-ray single-crystal diffraction. It crystallizes in the triclinic, space group P 1 with a = 8.8397(2), b = 13.327(3), c = 13.926(3) A, α = 63.27(3), β = 86.96(3), r = 80.68(3)°, V = 1445.6(5) A3, C49H51Cl2CuN12O2S6, Mr= 1166.82,Z=1, F(000) = 604, Dc = 1.340 g/cm3, μ = 0.735 mm-1, R = 0.0545 and wR = 0.1575 for 4521 observed reflections (I > 2σ(I)). X-ray analysis reveals that the Cu (II) ion is coordinated by two Cl- anions and two nitrogen atoms from different pyrimidine groups, forming a square structure.     

Synthesis,Crystal Structure and Photoluminescence of a Dinuclear Cuprous Complex with Thiocyanate Bridges

A cuprous dinuclear copper complex [PPh_2PAr_2Cu(μ-SCN)_2CuPPh_2PAr_2](1,PPh_2PAr_2 =(1-bis(2-methylphenyl)-phosphine-2-diphenylphosphino)benzene) was synthesized from the reaction of Cu SCN and PPh_2PAr_2 in CH_3CN at room temperature. The compound was characterized by Elemental Analysis,NMR,UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic,space group P1 with a = 10.225(2),b = 11.360(2),c = 13.420(3) ?,α = 95.81(3),β = 93.45(3),γ = 113.78(3)°,V = 1410.4(5) ?~3,Z = 1,Mr = 1192.21,Dc = 1.404 g/cm~3,F(000) = 616,μ = 3.029 mm~(–1),GOOF = 1.052,the final R = 0.0359,and w R = 0.0964 for 4878 observed reflections with I 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. The copper centers in the molecular structure are bridged by two thiocyanate anions and each Cu(I) is chelated further terminally by a PPh_2PAr_2 ligand. The [Cu(μ-SCN)_2Cu] cores have essential planar configurations. In the solid state,the complex exhibits blue photoluminescence with emission peaks λ_(max)= 478 nm(1),lifetimes 4.7 μs and quantum yields(ф = 0.43) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that it displays thermally activated delayed fluorescence at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ~(1,3)MLCT excited states.     

Crystal Structure and Photoluminescence of a Tetranuclear Cadmium Complex

A novel tetranuclear cadmium complex ([{Cd(C₁₅H₈O₇S)(H₂O)(DMSO)}₃{Cd(C₁₅H₈O₇S)(H₂O)₂}]·3DMSO·H₂O) was obtained by the self‐assembly of Cd(II) with 5,7‐dihydroxyflavone‐6‐sulfonate. The complex was characterized by ¹H NMR, IR, elemental analysis and X‐ray single‐crystal diffraction studies. It crystallizes in triclinic, space group $ P {\bar 1} $ . In the complex, the chelate atoms of Cd(II) are all from oxygen. Four Cd(II) are connected via the carbonyl and 5‐hydroxyanion of four ligands and form an approximate square. Four ligands locate at two sides of the square, and two of them at the same side are almost parallel and exist aromatic π‐π stacking. Ligands on the opposite side of the square are nearly perpendicular. The result of the luminescent studies indicated that the solid of the complex shwed photoluminescent properties because of a combination of coordination, hydrogen bonding and π‐π stacking interaction in the molecule structure. The complex emits green fluorescence (λ_em=496 nm) when it is excited at the wavelength of 440 nm.     

双核Cu(Ⅱ)—牛磺酸缩水杨醛席夫碱配合物的合成、晶体结构及生物活性

合成了双核铜配合物[Cu(TSSB)(H2O)]2.2H2O(TSSB=牛磺酸缩水杨醛席夫碱） ，通过元素分析，红外光谱对配合物进行了表征，并利用X射线法测定其结果，晶 体属三斜晶系，空间群P1，其晶胞参数为：a=0.69613(19)nm,b=0.9307(3)nm,c=1. 0439(3)nm;a=108.796(5)°,β=101.271(5)°,γ=105.617(5)°,V=0.5869(3) nm^3,Z=1,Dcald=1.849g/cm^3,μ=2.058nm^-1,F(000)=334，Gof=1.079,Δρ=379- 406e.nm^-3，两个铜原子配位数各为五，处于变形四方锥的配位环境中，并对配合 物进行了的生物活性试验，结果表明，配合物抗菌活性与青霉素接近，肿瘤抑制率 达63、5，半数臻死量为1000mg/kg,有可能成为一种新的抗菌、抗肿瘤药物。     

双核Cu(II)-牛磺酸缩水杨醛席夫碱配合物的合成、晶体结构及生物活性

合成了双核铜配合物 [Cu(TSSB) (H2 O) ] 2 ·2H2 O (TSSB =牛磺酸缩水杨醛席夫碱 ) ,通过元素分析、红外光谱对配合物进行了表征 ,并利用X射线法测定其结构 .晶体属三斜晶系 ,空间群P1- ,其晶胞参数为 :a =0 .69613 ( 19)nm ,b =0 .93 0 7( 3 )nm ,c=1.0 43 9( 3 )nm ;α =10 8.796( 5 )° ,β =10 1.2 71( 5 )° ,γ =10 5 .617( 5 )° ,V =0 .5 869( 3 )nm3 ,Z =1,Dcald=1.849g/cm3 ,μ =2 .0 5 8mm-1,F( 0 0 0 ) =3 3 4,Gof =1.0 79,Δρ =3 79～ -4 0 6e·nm-3 .两个铜原子配位数各为五 ,处于变形四方锥的配位环境中 .并对配合物进行了的生物活性试验 ,结果表明 ,配合物抗菌活性与青霉素接近 ,肿瘤抑制率达 63 .5 % .半数致死量为 10 0 0mg/kg .有可能成为一种新的抗菌、抗肿瘤药物     

Synthesis,Crystal Structure and Catechol Oxidase Mimic Activity of a Dinuclear Copper Complex

A dinuclear copper complex [Cu2LCl2](ClO4)2(L = 2,2'-(piperazine-1,4-diyl)bis-(N,N-bis(pyridine-2-ylmethyl)ethan-1-amine)) has been synthesized and structurally characterized. It crystallizes in triclinic, space group P1 with a = 8.5707(9), b = 10.5083(12), c = 11.4878(13), α = 76.197(2), β = 88.271(2), γ = 87.855(2)o, V = 1003.81(19)3, Z = 1, F(000) = 478, Dc = 1.544 Mg/m3, Mr = 933.60, μ = 1.383 mm-1, the final R = 0.0669 and wR = 0.1486 for 3675 observed reflections with I 2ρ(I). Its catechol oxidase mimic activity was studied spectroscopically by using 3,5-di-tert-butylcatechol(3,5-DTBC) as the substrate. The results showed that the kinetics of catechol catalyzed by the complex accorded with the Michaelis-Mentent equation, and the catechol oxidase catalytic activity of the complex increased with increasing the pH values.     

Synthesis, Crystal Structure and Biological Activity of a Planar Copper Complex Derived from S-benzyldithiocarbazate

A planar transition metal complex Cu(L)2 (L = (E)-benzyl-2-(4-nitrobenzylidene)-hydrazinecarbodithioate) has been prepared and determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system,space group P21/c with a = 6.7101(11),b = 16.952(3),c = 13.962(3) ,β = 92.458(4)°,V = 1586.7(5) 3,Z = 4,Mr = 724.33,Dc = 1.516 g·m-3,μ = 0.998 mm-1,F(000) = 742,S = 1.021,R = 0.0634 and wR = 0.1077 for 813 observed reflections with Ⅰ 2σ(Ⅰ) and 205 parameters. In the molecular structure of the title complex,the copper atom exhibits a slightly distorted square-planar geometry in which the basal plane is defined by two N and two S atoms from two bidentate ligands. The complex was evaluated for its antitumor activity against two kinds of cell lines (MKN45 and HepG2) by MTT method. The preliminary bioassay indicates that the complex exhibits weak antitumor activity.     

Synthesis,Crystal Structure and Photoluminescence of a New Cd-organic meso-Helicate

One-pot solvothermal reaction of transition metal Cd(Ⅱ) salt with (2E,2’E)-3,3’-((propane-1,3-diylbis(oxy))bis(2,1-phenylene))diacrylic acid (H2ppa) and 1,10-phenanthroline (phen) generates a meso-helicate, [Cd(ppa)(phen)(H2O)]2, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent property. The complex crys-tallizes in monoclinic, space group P21/c with a = 13.4622(7), b = 24.8452(12), c = 8.9314(4) , β = 97.564(1)o, V = 2961.3(2) 3, C66H56N4O14Cd2, Mr = 1353.97, Dc = 1.518 g/cm3, μ(MoKα) = 0.789 mm-1, F(000) = 1376, Z = 2 , the final R = 0.0248 and wR = 0.0667 for 4673 observed reflections (I > 2σ(I)). The 1-D supramolecular chain is built up from the complex by π-π stacking interactions, and inter-chain hydrogen bonds prompt the 1-D chains into a 2-D layer. The title compound shows strong photoluminescence with emission maximum at λ = 445 nm upon λEx, max = 240 nm.     

四核铜化合物(Cu4L4)(CH3CN)(H2L=(R)-1-(1-羟基正丁烷-2-氨甲基)萘-2-醇)的合成、晶体结构及磁性质

采用具有手性的席夫碱配体，(R)-1-(1-羟基正丁烷-2-氨甲基)萘-2-醇(H₂L)，和醋酸铜反应得到四核铜的化合物(Cu₄L₄)(CH₃CN)。用X-射线衍射对化合物的晶体结构进行了测定，结果表明此化合物含有4个铜和4个配体，铜通过配位作用和4个氧原子形成类立方烷中心。磁性测定表明此化合物中金属离子之间有弱的反铁磁相互耦合作用。     

双核铜(Ⅰ)配合物的合成、晶体结构与性质研究

本文合成了1个新的铜双核配合物[(CuI)(PMN)]2.2CH3CN(PMN=2、4-二氨基-5-氯苯基-6-乙基嘧啶),并且通过元素分析、红外、荧光、热重和单晶X-射线进行了表征。该配合物属三斜晶系,空间群P1,a=0.8100(16)nm,b=0.96950(19)nm,c=1.2049(2)nm,α=97.88(3)°,β=93.31(3)°,γ=94.14(3)°,V=0.933 8(3)nm3,Z=1,R=0.037 1。在配合物中,每个Cu(Ⅰ)离子与PMN配体的1个N原子和2个I原子配位,展示出三角几何构型。相邻的2个Cu(Ⅰ)离子通过碘原子相连形成双核铜配合物,并进一步通过氢键和I…I作用形成三维网状结构。     

二苄基锡水杨醛缩邻氨基苯酚Schiff碱配合物的合成、结构及荧光性质研究

二苄基二氯化锡和水杨醛缩邻氨基苯酚Schiff碱按物质的量比1∶1反应,合成了二苄基锡水杨醛邻缩氨基苯酚Schiff碱配合物。经X-射线衍射方法测定了其晶体结构,属单斜晶系,空间群为P21/n,晶体学参数a=1.110 03(3)nm,b=1.719 87(5)nm,c=1.176 09(3)nm,β=100.564 0(10)°,V=2.207 23(10)nm3,Z=4,Dc=1.541 g·cm-3,μ(Mo Kα)=11.81 cm-1,F(000)=1 023,R1=0.026 8,wR2=0.061 9,中心锡原子为五配位的畸变三角双锥构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。研究了配合物的荧光性质。     

Synthesis and Crystal Structure of aNovel Polymer Copper（ Ⅱ） Complex

1 INTRODUCTION One-dimensional coordination polymers of metal complexes have been extensively studied for many years owing to their unusual properties, and many efforts have been made to prepare these kinds of complexes. Study on these polymer complexes has an active field of coordination chemistry in recent years[1～5]. In this study we obtained a com- plex C14H9CuNO3CH3OH, of which the carboxy- late oxygen atom acts as the bridging ligands to coordinate to the second metal atom, fo…     

二苄基锡水杨醛缩邻氨基苯酚Schiff碱配合物的合成、结构及荧光性质研究

二苄基二氯化锡和水杨醛缩邻氨基苯酚Schiff碱按物质的量比1:1反应, 合成了二苄基锡水杨醛邻缩氨基苯酚Schiff碱配合物。经X-射线衍射方法测定了其晶体结构, 属单斜晶系, 空间群为P2₁/n, 晶体学参数a=1.110 03(3) nm, b=1.719 87(5) nm, c=1.176 09(3) nm, β=100.564 0(10)°, V=2.207 23(10) nm³, Z=4, D_c=1.541 g·cm^-3, μ(Mo Kα)=11.81 cm^-1, F(000)=1 023, R₁=0.026 8, wR₂=0.061 9, 中心锡原子为五配位的畸变三角双锥构型。对其结构进行量子化学从头计算, 探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。研究了配合物的荧光性质。     

三核铜(Ⅰ)配合物合成及结构分析

铜(I)配合物由于其变化奇异的结构,性质及配位数而引起化学工作者的广泛兴趣.众所周知,四电子供体双二苯基膦甲烷(dppm)适宜在近距离内与两个金属原子同时配位,容易形成八员环的二聚体M2P4C2[1],因而是桥联两个低氧化态过渡金属的最佳选择,由于在M2(dppm)2框架结构中的配位不饱和性,仍需有单齿或双齿配体参加配位,这也正是M2(dppm)2类配合物特殊的成键,反应性和催化性的主要原因,这种附加配体不仅影响金属离子的配位构型而且影响M2(dppm)2的框架结构,同时dppm能够稳定多核配合物.我们在配体dppm存在下直接还原铜(Ⅱ)盐得到双核铜(I)配合物[Cu(dppm)(NO3)]2[2],又在四苯基硼钠存在下部分取代弱配位的硝酸根制备了具有新奇结构的三核铜(I)配合物[Cu3(dppm)3(OH)(NO3)](NO3)CH3OH,通过元素分析,核磁,红外,电导等方法研究了配合物的有关物理化学性质,配合物的晶体和分子结构已由X-射线单晶结构分析确定.     

Synthesis,Crystal Structure and Magnetic Properties of a Novel Copper Inverse-9-metallacrown-3 Complex

<正>The reaction of phenyl 2-pyridyl ketoxime(PhPyCNOH)with Cu(NO_3)_2·3H_2O has led to a triangular complex Cu_3(OH)(PhPyCNO)_3(NO_3)·NO_3·H_2O 1 containing the[Cu_3(μ_2-OH)]~(5+) core and possessing the very rare inverse 9-metallacrown-3 motif created by the bridging oximate groups.Crystallographic data for 1:C_(36_H_(30)N_8O_(11)Cu_3,M_r=941.30,monoclinic,space group C2/c,a =18.815(9),b=33.888(15),c=14.307(7)(?),β=118.945(6)°,V=7983(6)(?)~3,Z=8,D_c=1.566 g/cm~3,n=1.652 mm~(-1),F(000)= 3816,R= 0.0644 and wR= 0.1393 for 3468 observed reflections(I2σ(I)).Preliminary variable-temperature magnetic susceptibility studies reveal an antiferroma-gnetically -coupled system showing antisymmetric exchange.