A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic ligh...We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.展开更多
Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal s...Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.展开更多
A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in...A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.展开更多
A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b =...A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.展开更多
Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and...Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.展开更多
The availability of chemical and biological data presented in this paper is the basis for understanding not only the current state of anti-cancer drugs based on gold(Ⅲ),but also the rationale for strategies for futur...The availability of chemical and biological data presented in this paper is the basis for understanding not only the current state of anti-cancer drugs based on gold(Ⅲ),but also the rationale for strategies for future drug design.New Au(Ⅲ)nanosized complexes of cefotaxime(ceph-3)and cefepime(ceph-4)ligands as a 3rd and 4th of cephalosporin generation drugs were synthesized.Gold(Ⅲ)complexes were discussed based on the elemental,molar conductance,thermal and magnetic moment measurements as well as spectral(FTIR,1HNMR,UV-Vis,and XRD)techniques.FT-IR spectra revealed that the ceph-3 and ceph-4 ligands reacted as a bidentate ligands through carboxylate oxygen andβ-lactam oxygen groups.The analytical analysis confirm that the molar ratio is 1∶1(Au 3+/ceph)with general formula[Au(L)(Cl)2]where L=ceph-3 or ceph-4.The structures of Au(Ⅲ)complexes were presence as a square planar geometry.X-ray diffraction patterns referred to a crystalline nature for all synthesized complexes.TEM analyses confirmed that the synthetic gold(Ⅲ)complexes have a nanosized particles.In vitro antimicrobial activities of Au(Ⅲ)complexes were evaluated towards two types of bacteria(G+&G-).The antitumor activities of gold(Ⅲ)complexes are appraised against breast(MCF-7)and colorectal adenocarcinoma(Caco-2)cell lines,which means that the two complexes may consider promising anticancer drugs.展开更多
In this paper, the title complex K[In Ⅲ(Hdtpa)]·3.5H 2O(dtpa=diethylenetriaminepentaacetic acid) was synthesized and its crystal structure was determined by single crystal X ray structure analysis. The crystal b...In this paper, the title complex K[In Ⅲ(Hdtpa)]·3.5H 2O(dtpa=diethylenetriaminepentaacetic acid) was synthesized and its crystal structure was determined by single crystal X ray structure analysis. The crystal belongs to monoclinic system, P 2 1/ c (No.14) space group with a =0.978 1(2) nm, b =0.733 8(1) nm , c =2.962 9(6) nm, β =91.81(3)°, V =0.212 6(1) nm 3, Z =4, M =606.31, D x=1.895 g·cm -3 , μ =1.382 1 mm -1 , F (000)=1 228, R =0.035 and R w=0.041 for 2 802 unique reflections. The complex anion [In Ⅲ(Hdtpa)] - has a pseudo monocapped trigonal prismatic seven coordination structure in which the seven coordinate atoms, three N and four O atoms, are all from a ligand dtpa. In addition, it can be seen that the complex anion [In Ⅲ(Hdtpa)] - can furnish a free carboxyl group(—CH 2COOH) being used for molecular embellishment to form the target diagnosis and treat drug of anticancer. [WT5HZ]展开更多
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
文摘We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.
文摘Three efficient methods for the synthesis of a series of Cu(Ⅱ) and Cu(Ⅰ) complexes based on imidazo[1,5-a]pyridine derivatives were developed.These methods include the following:(ⅰ)Cu(Ⅱ) salts were used as metal sources and N,N-dimethylformamide was employed as a solvent as well as a reductant to produce Cu(Ⅰ) complexes.(ⅱ) An iodide-containing compound was utilized as a ligand and iodide source to prepare complexes.An in situ metalligand reaction occurred and an iodide-bridged copper complex was generated.(ⅲ) A series of aldehydes were added to the reaction systems to induce in situ metal-ligand reactions between the aldehydes and the imidazo[1,5-a]pyridine derivatives,producing polydentate ligand scaffolds.Eight complexes were prepared and characterized.The catalytic activities of these complexes toward the ketalization of ketones by ethylene glycol were investigated.With the exception of complex4,the remaining seven complexes all showed high catalytic activity.The lower activity of 4 may be due to the larger radius of bridging iodide ions and the shorter Cu(Ⅰ)…Cu(Ⅰ) distance.CCDC:2357696,1·2CH_(2)Cl_(2);2357697,2;2018292,3;2092192,4;2092190,5;2155557,6;2406155,7;2406156,8·EtOH.
文摘A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.
基金Project(21001118)supported by National Natural Science Foundation of ChinaProject(12JJ3016)supported by Natural Science Foundation of Hunan Province,China
文摘A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.
基金Project(20761002) supported by the National Natural Science Foundation of China
文摘Two novel ligands named 4-styrylpyridine-2,6-dicarboxylic acid (4-SPDA) and 4-(4-(2-(2, 6-dicarboxypyridin-4-yl)- vinyl)styryl)pyridine-2,6-dicarboxylic acid(DSPDA) and their complexes with Tb(Ⅲ) were synthesized and characterized by infrared spectrometry, 1H nuclear magnetic resonance, elemental analysis and gas chromatograph-mass spectrometry. The ligand synthetic route was optimized. The fluorescence properties of the complex in solid state, in different kind of solvents and in solutions with different pH values were investigated in detail. The results show that the yields of DSPDA and 4-SPDA reach over 78% by Wittig-Horner reaction and other eight pyridine-2, 6-dicarboxylic acid derivatives with different substituents on pyridine ring, and their complexes with Tb(Ⅲ) are also obtained. The fluorescence intensities of the complexes with electron-donating groups are more intense than those of the complexes with electron-withdrawing groups on pyridine ring; fluorescence intensities of the complexes are the strongest in neutral solution (pH=7), and the less the dipole moment of solvent molecule is, the stronger the fluorescence intensity is. It is found that the two ligands (4-APDA and DSPDA) are the good sensitizers for Tb(Ⅲ) ion.
基金the Deanship of Scientific Research at Princess Nourah bint Abdulrahman University,through the Research Funding Program(#RFP-1440-3)。
文摘The availability of chemical and biological data presented in this paper is the basis for understanding not only the current state of anti-cancer drugs based on gold(Ⅲ),but also the rationale for strategies for future drug design.New Au(Ⅲ)nanosized complexes of cefotaxime(ceph-3)and cefepime(ceph-4)ligands as a 3rd and 4th of cephalosporin generation drugs were synthesized.Gold(Ⅲ)complexes were discussed based on the elemental,molar conductance,thermal and magnetic moment measurements as well as spectral(FTIR,1HNMR,UV-Vis,and XRD)techniques.FT-IR spectra revealed that the ceph-3 and ceph-4 ligands reacted as a bidentate ligands through carboxylate oxygen andβ-lactam oxygen groups.The analytical analysis confirm that the molar ratio is 1∶1(Au 3+/ceph)with general formula[Au(L)(Cl)2]where L=ceph-3 or ceph-4.The structures of Au(Ⅲ)complexes were presence as a square planar geometry.X-ray diffraction patterns referred to a crystalline nature for all synthesized complexes.TEM analyses confirmed that the synthetic gold(Ⅲ)complexes have a nanosized particles.In vitro antimicrobial activities of Au(Ⅲ)complexes were evaluated towards two types of bacteria(G+&G-).The antitumor activities of gold(Ⅲ)complexes are appraised against breast(MCF-7)and colorectal adenocarcinoma(Caco-2)cell lines,which means that the two complexes may consider promising anticancer drugs.
文摘In this paper, the title complex K[In Ⅲ(Hdtpa)]·3.5H 2O(dtpa=diethylenetriaminepentaacetic acid) was synthesized and its crystal structure was determined by single crystal X ray structure analysis. The crystal belongs to monoclinic system, P 2 1/ c (No.14) space group with a =0.978 1(2) nm, b =0.733 8(1) nm , c =2.962 9(6) nm, β =91.81(3)°, V =0.212 6(1) nm 3, Z =4, M =606.31, D x=1.895 g·cm -3 , μ =1.382 1 mm -1 , F (000)=1 228, R =0.035 and R w=0.041 for 2 802 unique reflections. The complex anion [In Ⅲ(Hdtpa)] - has a pseudo monocapped trigonal prismatic seven coordination structure in which the seven coordinate atoms, three N and four O atoms, are all from a ligand dtpa. In addition, it can be seen that the complex anion [In Ⅲ(Hdtpa)] - can furnish a free carboxyl group(—CH 2COOH) being used for molecular embellishment to form the target diagnosis and treat drug of anticancer. [WT5HZ]
