A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-yl)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its plati...A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-yl)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its platinum complex were investigated. A characteristic metal-ligand charge transfer absorption peak at 439 nm in the UV spectrum and a strong emission peak at 625 nm in the photoluminescence spectrum were observed for this complex in dichloromethane. Cyclic voltammtry (CV) analysis shows that the EHOMO (energy level of the highest occupied molecular orbital) and ELUMO (energy level of the lowest unoccupied molecular orbital) of the platinum complex are about 、5.69 and 、3.25 eV, respectively, indicating that the oxadiazole-based platinum complex has a potential application in electrophosphorescent devices used as a red-emitting material.展开更多
The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mo...The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO 3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.展开更多
Seven novel platinum （Ⅱ） complexes [ Pt（Ⅱ） （NH3） （CH3NH2）X2] （Ⅰ-Ⅶ ） （ X： CH3COO^-, CH2CICOO^- , CHCI2COO^- , C6H5-COO^- , p-CH3O--C6H4-COO^- , p-NH2-C6H4-COO^- , p-NO2--C6H4- COO^-） were prepared and ...Seven novel platinum （Ⅱ） complexes [ Pt（Ⅱ） （NH3） （CH3NH2）X2] （Ⅰ-Ⅶ ） （ X： CH3COO^-, CH2CICOO^- , CHCI2COO^- , C6H5-COO^- , p-CH3O--C6H4-COO^- , p-NH2-C6H4-COO^- , p-NO2--C6H4- COO^-） were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis, IR, UV, and ^1H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence： cisplatin 〉 Ⅳ 〉 Ⅴ 〉 Ⅵ 〉 Ⅶ 〉 Ⅰ 〉 Ⅱ 〉 Ⅲ. Moreover, the complexes （ Ⅰ --Ⅻ） display substantially greater activities agaist EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.展开更多
Organoplatinum（Ⅱ） compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent appro...Organoplatinum（Ⅱ） compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent approach to create well-ordered supramolecular architectures with tunable properties,which underpin the role of solvent-directed approach for the design of functional materials.In this minireview,the recent advances on supramolecular self-assembly of cyclometalated platinum（Ⅱ） complexes have been discussed.During the self-assembly process,non-covalent Pt-Pt and π-π interactions play crucial roles in controlling the structures and functions of the resulting assemblies.展开更多
A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppy...A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.展开更多
Two luminescent hetero-trinuclear complexes [Pt2Cu（μ-dpppy）2（C≡CC6H4R-4）4]（Cl O4）（R = H,1;R = CH3,2;dpppy = 2,6-bis（diphenylphosphino）pyridine） have been synthesized and characterized by elemental analyses...Two luminescent hetero-trinuclear complexes [Pt2Cu（μ-dpppy）2（C≡CC6H4R-4）4]（Cl O4）（R = H,1;R = CH3,2;dpppy = 2,6-bis（diphenylphosphino）pyridine） have been synthesized and characterized by elemental analyses,ESI-MS,^1H and ^31P{^1H} NMR spectroscopy,and X-ray crystallography for 2.Their photophysical properties in the solid state and in solutions at room temperature and in frozen glasses at 77 K were studied.Both complexes 1 and 2 show strong orange-red emission in the solid state at room temperature and in frozen glasses at 77 K,and weak emission in solutions.展开更多
The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane,...The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.展开更多
A series of luminescent cyclometalated platinum(II) complexes, (C^N^N)Pt(C≡CR) [HC^N^N=4 (4 tolyl) 6 phenyl 2,2′ bipyridine; R=4 chlorophenyl (1), phenyl (2) and 4 tolyl (3)], were synthesized, and their...A series of luminescent cyclometalated platinum(II) complexes, (C^N^N)Pt(C≡CR) [HC^N^N=4 (4 tolyl) 6 phenyl 2,2′ bipyridine; R=4 chlorophenyl (1), phenyl (2) and 4 tolyl (3)], were synthesized, and their spectroscopic properties have been examined. These complexes are brightly emissive both in fluid solution and in the solid state, attributed to triplet metal to ligand charge transfer ( 3MLCT) state. The excited state energy can be tuned by ancillary acetylide ligands. The emission lifetimes in dichloro^methane solution at room temperature were up to 1 64 μs and the emission quantum yields were in the range of 0 03-0 15.展开更多
Cis-diaminedithiocyanatoplatinum(Ⅱ)(cis-[Pt(SCN)2(NH3)2])was prepared and characterized through content analysis of Pt,MS,IR.The results show that the complex has cis configuration and the bond type of Pt and SCN-is ...Cis-diaminedithiocyanatoplatinum(Ⅱ)(cis-[Pt(SCN)2(NH3)2])was prepared and characterized through content analysis of Pt,MS,IR.The results show that the complex has cis configuration and the bond type of Pt and SCN-is Pt-S.When the aqueous solution of the complex was stored for one week,an orange-yellow precipitation appeared,different from the complex with light yellow color.Further comparative studies of these two complexes suggested that the precipitation is cis-[Pt(NCS)2(NH3)2],the linkage isomerism of cis-[Pt(SCN)2(NH3)2].The mechanism of the isomerism reaction is also discussed.展开更多
基金Project(50473046) supported by the National Natural Science Foundation of ChinaProject(204097) supported by the Science Foundation of the Ministry of Education of China+1 种基金Project(04JJ1002) supported by the Outstanding Youth Foundation of Hunan Province,ChinaProject(06JJ2008) supported by the Natural Science Foundation of Hunan Province,China
文摘A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-yl)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its platinum complex were investigated. A characteristic metal-ligand charge transfer absorption peak at 439 nm in the UV spectrum and a strong emission peak at 625 nm in the photoluminescence spectrum were observed for this complex in dichloromethane. Cyclic voltammtry (CV) analysis shows that the EHOMO (energy level of the highest occupied molecular orbital) and ELUMO (energy level of the lowest unoccupied molecular orbital) of the platinum complex are about 、5.69 and 、3.25 eV, respectively, indicating that the oxadiazole-based platinum complex has a potential application in electrophosphorescent devices used as a red-emitting material.
基金Supported by the Foundation of Academ y L eader of Zhejiang Gongshang U niversity(No.19972 0 0 2 )
文摘The stability constants of some ternary mixed-ligand complexes, Pt(Phen)(CA)+, where Phen=1,10-phenanthroline and CA- =carboxylate, were determined by means of potentiometric pH titration in aqueous solutions(I=0.1 mol/L, KNO 3; 25 ℃), and the stability of them was compared with that of the corresponding binary complexes. It was revealed that the ternary complexes containing phenylalkane carboxylates ligands(PCA-) are much more stable than those formed with formate and acetate. The results indicate that there exist the intramolecular aromatic-ring interactions between the phenanthroline ring of Phen and the phenyl moiety of ligand PCA- in the ternary mixed-ligand Pt(Phen)(PCA)- complexes. The extent of the stacking interactions, which depends on the number of methylene groups between the phenyl moieties and the coordinated phenylalkane carboxylate groups, was calculated. The best-fitted stack was obtained for the complexes with 2-phenylacetate and 3-phenylpropionate as the ligands.
文摘Seven novel platinum （Ⅱ） complexes [ Pt（Ⅱ） （NH3） （CH3NH2）X2] （Ⅰ-Ⅶ ） （ X： CH3COO^-, CH2CICOO^- , CHCI2COO^- , C6H5-COO^- , p-CH3O--C6H4-COO^- , p-NH2-C6H4-COO^- , p-NO2--C6H4- COO^-） were prepared and characterized by means of elemental analysis, molar conductivity, thermal analysis, IR, UV, and ^1H NMR spectrometries. The cytotoxicity against HCT-8, BGC-823, MCF-7, EJ, and HL-60 cell lines increases in the following sequence： cisplatin 〉 Ⅳ 〉 Ⅴ 〉 Ⅵ 〉 Ⅶ 〉 Ⅰ 〉 Ⅱ 〉 Ⅲ. Moreover, the complexes （ Ⅰ --Ⅻ） display substantially greater activities agaist EJ and HL-60 cell lines than those against the cell lines from other carcinomas. They can induce a concentration-dependent accumulation of HL-60 cells in the G2/M phase of the cell cycle as cisplatin. There is no significant correlation between total DNA platination levels and cytotoxicity of the complexes.
基金supported by the National Natural Science Foundation of China(No.21274139)the Fundamental Research Funds for the Central Universities(Nos.WK3450000001,WK2060200012)
文摘Organoplatinum（Ⅱ） compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent approach to create well-ordered supramolecular architectures with tunable properties,which underpin the role of solvent-directed approach for the design of functional materials.In this minireview,the recent advances on supramolecular self-assembly of cyclometalated platinum（Ⅱ） complexes have been discussed.During the self-assembly process,non-covalent Pt-Pt and π-π interactions play crucial roles in controlling the structures and functions of the resulting assemblies.
基金support from the National Natural Science Foundation of China (Grant No. 20472060)the Basic Research Foundation of Sichuan Province,China (Grant No. 07JY029-015)
文摘A new series of mono-cyclometalated square planar platinum(Ⅱ) complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O is β-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ) complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction of π-π interactions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs) and even for nondoped PhOLEDs.
基金Supported by NSF of Fujian Province(No.2014J01046)Key Science Project(type A)of the Fujian Provincial Department of Education,China(No.JA12021)the NSF for Fostering Talents in Basic Research of China(No.J1103303)
文摘Two luminescent hetero-trinuclear complexes [Pt2Cu（μ-dpppy）2（C≡CC6H4R-4）4]（Cl O4）（R = H,1;R = CH3,2;dpppy = 2,6-bis（diphenylphosphino）pyridine） have been synthesized and characterized by elemental analyses,ESI-MS,^1H and ^31P{^1H} NMR spectroscopy,and X-ray crystallography for 2.Their photophysical properties in the solid state and in solutions at room temperature and in frozen glasses at 77 K were studied.Both complexes 1 and 2 show strong orange-red emission in the solid state at room temperature and in frozen glasses at 77 K,and weak emission in solutions.
文摘The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.
文摘A series of luminescent cyclometalated platinum(II) complexes, (C^N^N)Pt(C≡CR) [HC^N^N=4 (4 tolyl) 6 phenyl 2,2′ bipyridine; R=4 chlorophenyl (1), phenyl (2) and 4 tolyl (3)], were synthesized, and their spectroscopic properties have been examined. These complexes are brightly emissive both in fluid solution and in the solid state, attributed to triplet metal to ligand charge transfer ( 3MLCT) state. The excited state energy can be tuned by ancillary acetylide ligands. The emission lifetimes in dichloro^methane solution at room temperature were up to 1 64 μs and the emission quantum yields were in the range of 0 03-0 15.
基金supported by the National Natural Science Foundation of China(21073143)“Chunhui Project”from the Ministry of Education of China(Z2009-1-71002,Z2009-1-71006)+2 种基金Graduate Starting Seed Fund of Northwestern Polytechnical University(NPU),China(Z2015152)NPU Foundation for Graduate InnovationChina~~
文摘Cis-diaminedithiocyanatoplatinum(Ⅱ)(cis-[Pt(SCN)2(NH3)2])was prepared and characterized through content analysis of Pt,MS,IR.The results show that the complex has cis configuration and the bond type of Pt and SCN-is Pt-S.When the aqueous solution of the complex was stored for one week,an orange-yellow precipitation appeared,different from the complex with light yellow color.Further comparative studies of these two complexes suggested that the precipitation is cis-[Pt(NCS)2(NH3)2],the linkage isomerism of cis-[Pt(SCN)2(NH3)2].The mechanism of the isomerism reaction is also discussed.
