Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysi...Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm, both complexes were found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form Ⅰ to nicked form Ⅱ. The mechanism studies reveal that singlet oxygen 1O2 and hydroxyl radical (OH-) play a significant role in the photocleavage process.展开更多
Amphiphilic polypyridyl mthenium（Ⅱ） complex cis-di（isothiocyanato）（4,4＇-di-tert-butyl-2,2＇-bipyridyl）（4,4＇- dicarboxy-2,2＇-bipyridyl）ruthenium（Ⅱ）（K005） has been synthesized and characterized by cycli...Amphiphilic polypyridyl mthenium（Ⅱ） complex cis-di（isothiocyanato）（4,4＇-di-tert-butyl-2,2＇-bipyridyl）（4,4＇- dicarboxy-2,2＇-bipyridyl）ruthenium（Ⅱ）（K005） has been synthesized and characterized by cyclic voltammetry, ^1H NMR, UV-Vis, and FT-IR spectroscopies. The sensitizer sensitizes TiO2 over a notably broad spectral range due to its intense metal-to-ligand charge-transfer （MLCT） bands at 537 and 418 nm. The photophysical and photochemical studies of K005 were contrasted with those of cis-Ru（dcbpy）2（NCS）2, known as the N3 dye, and the amphiphilic ruthenium（Ⅱ） dye Z907. A reversible couple at E1/2=0.725 V vs. saturated calomel electrode （SCE） with a separation of 0.08 V between the anodic and cathodic peaks, was observed due to the Ru^Ⅱ/Ⅲ couple by cyclic voltammetry. Furthermore, this amphiphilic ruthenium complex was successfully used as sensitizers for dye-sensitized solar cells with the efficiency of 3.72% at the 100 mW·cm^-2 irradiance of air mass 1.5 simulated sunlight without optimization of TiO2 films and the electrolyte.展开更多
Three Ru(Ⅱ) complexes [Ru(bpy)2(1-IQTNH)](ClO4)2 (1), [Ru(bpy)2(2-QTNH)](ClO4)2 (2) and [Ru(bpy)2(3-IQTNH)](ClO4)2 (3) (bpy = 2,2′-bipyridine, 1-IQTNH = 6-(isoquinolin-1-yl)-1,3,5-triazine-2,4-diamine, 2-QTNH = 6-(q...Three Ru(Ⅱ) complexes [Ru(bpy)2(1-IQTNH)](ClO4)2 (1), [Ru(bpy)2(2-QTNH)](ClO4)2 (2) and [Ru(bpy)2(3-IQTNH)](ClO4)2 (3) (bpy = 2,2′-bipyridine, 1-IQTNH = 6-(isoquinolin-1-yl)-1,3,5-triazine-2,4-diamine, 2-QTNH = 6-(quinolin-2-yl)-1,3,5-triazine-2,4-diamine, 3-IQTNH = 6-(isoquinolin-3-yl)-1,3,5-triazine-2,4-diamine) have been synthesized and characterized by elemental analysis, 1H NMR spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The electrochemical and spectroscopic properties of the complexes differ from those of [Ru(bpy)3]2+ owing to the structural differences between the ligands and their complexes.展开更多
A novel Ru(Ⅱ) tris-bipyridyl complex, Ru(bpy)2[bpy(CO2H)(CO2Et)][PF6]2 is prepared in a simple and convenient process. It will be an alternativ?of Ru(bpy)2bpy(CO2Et)2(PF6)2 to be used in solar cel須 as photosensitive...A novel Ru(Ⅱ) tris-bipyridyl complex, Ru(bpy)2[bpy(CO2H)(CO2Et)][PF6]2 is prepared in a simple and convenient process. It will be an alternativ?of Ru(bpy)2bpy(CO2Et)2(PF6)2 to be used in solar cel須 as photosensitive dyes.展开更多
The interactions between two trinuclear Ru（II） complexes and calf thymus DNA（CT DNA） were studied via absorption spectroscopy, reverse salt titrations, binding stoichiometry, DNA melting experiments, as well as vi...The interactions between two trinuclear Ru（II） complexes and calf thymus DNA（CT DNA） were studied via absorption spectroscopy, reverse salt titrations, binding stoichiometry, DNA melting experiments, as well as viscosity measurement. The results indicate that complexes 1 and 2 bind to DNA via the interaction of the planar π-delocalized system of the complexes with intrinsic binding constants of 4.18 × 10^5 and 3.85 × 10^6 L/tool, respectively, and non-electrostatic binding free energy makes a predominant contribution to the binding free energy. The in vitro cytotoxic activity of complexes 1 and 2 was evaluated by the MTT[3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyl- 2H-tetrazolium bromide] method. Complex I shows higher anticancer potency than complex 2 against four tumor cell lines. Further mechanism study indicates that complexes 1 and 2 can cause cell cycle arrest in the G2/M phase.展开更多
13C and 99Ru-NMR chendcal shifts are reported for the ruthenium(II) tris complexes of5-substitUted 1,10-phenanthrolines. It has been found that both of them are affected by the substituents on the phenanthrolines in a...13C and 99Ru-NMR chendcal shifts are reported for the ruthenium(II) tris complexes of5-substitUted 1,10-phenanthrolines. It has been found that both of them are affected by the substituents on the phenanthrolines in a direction consistent with that expected from the electron withdrawing ability of the substituent.展开更多
The two mixed ligand complexes, cis [Ru(mnt)(bpy)2] (1) and cis [Ru (dmit)(bpy)2] (2) (where mnt2- is maleonitriledithiolate and dmit2- reprents 4,5 dimercapto 1,3 dithiole 2 thione), have been synthesized and charact...The two mixed ligand complexes, cis [Ru(mnt)(bpy)2] (1) and cis [Ru (dmit)(bpy)2] (2) (where mnt2- is maleonitriledithiolate and dmit2- reprents 4,5 dimercapto 1,3 dithiole 2 thione), have been synthesized and characterized by element analysis and IR spectra. The electronic spectra of 1 and 2 in DMF solutions showed that the two complexes have broad absorption charge transfer bands [LMCT i.e. charge transfer from dithiolate to Ru? or LL′CT, that is, charge transfer from dithiolate to 2,2′ bipyridine] in the visible region. Compared with 1, the LMCT or LL′CT band for 2 shifts to low frequency. The results of electrochemistry of the two complexes in DMF are consistent with that of the electronic spectra.展开更多
基金Supported by the 973 Program of China (Grant No 2007CB815306)the National Natural Science Foundation of China (Grant Nos 20771105 & 20871122)+2 种基金the Pro-gram for New Century Excellent Talents in University (Grant No NCET-06-0718)the Key Project (Grant No 108103) of Ministry of Educationthe Natural Sci-ence Foundation of Guangclong Province (Grant No 9351027501000003)
文摘Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm, both complexes were found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form Ⅰ to nicked form Ⅱ. The mechanism studies reveal that singlet oxygen 1O2 and hydroxyl radical (OH-) play a significant role in the photocleavage process.
文摘Amphiphilic polypyridyl mthenium（Ⅱ） complex cis-di（isothiocyanato）（4,4＇-di-tert-butyl-2,2＇-bipyridyl）（4,4＇- dicarboxy-2,2＇-bipyridyl）ruthenium（Ⅱ）（K005） has been synthesized and characterized by cyclic voltammetry, ^1H NMR, UV-Vis, and FT-IR spectroscopies. The sensitizer sensitizes TiO2 over a notably broad spectral range due to its intense metal-to-ligand charge-transfer （MLCT） bands at 537 and 418 nm. The photophysical and photochemical studies of K005 were contrasted with those of cis-Ru（dcbpy）2（NCS）2, known as the N3 dye, and the amphiphilic ruthenium（Ⅱ） dye Z907. A reversible couple at E1/2=0.725 V vs. saturated calomel electrode （SCE） with a separation of 0.08 V between the anodic and cathodic peaks, was observed due to the Ru^Ⅱ/Ⅲ couple by cyclic voltammetry. Furthermore, this amphiphilic ruthenium complex was successfully used as sensitizers for dye-sensitized solar cells with the efficiency of 3.72% at the 100 mW·cm^-2 irradiance of air mass 1.5 simulated sunlight without optimization of TiO2 films and the electrolyte.
基金supported by the National Basic Research Program of China (2007CB815306)the National Natural Science Foundation of China (20771105, 20871122)+1 种基金the Key Project of Ministry of Education (108103)the Natural Science Foundation of Guangdong Province (9351027501000003)
文摘Three Ru(Ⅱ) complexes [Ru(bpy)2(1-IQTNH)](ClO4)2 (1), [Ru(bpy)2(2-QTNH)](ClO4)2 (2) and [Ru(bpy)2(3-IQTNH)](ClO4)2 (3) (bpy = 2,2′-bipyridine, 1-IQTNH = 6-(isoquinolin-1-yl)-1,3,5-triazine-2,4-diamine, 2-QTNH = 6-(quinolin-2-yl)-1,3,5-triazine-2,4-diamine, 3-IQTNH = 6-(isoquinolin-3-yl)-1,3,5-triazine-2,4-diamine) have been synthesized and characterized by elemental analysis, 1H NMR spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The electrochemical and spectroscopic properties of the complexes differ from those of [Ru(bpy)3]2+ owing to the structural differences between the ligands and their complexes.
文摘A novel Ru(Ⅱ) tris-bipyridyl complex, Ru(bpy)2[bpy(CO2H)(CO2Et)][PF6]2 is prepared in a simple and convenient process. It will be an alternativ?of Ru(bpy)2bpy(CO2Et)2(PF6)2 to be used in solar cel須 as photosensitive dyes.
基金Supported by the National Natural Science Foundation of China（No.21301034） and the Natural Science Foundation of Guangdong Province, China（No.S2013040014083）.
文摘The interactions between two trinuclear Ru（II） complexes and calf thymus DNA（CT DNA） were studied via absorption spectroscopy, reverse salt titrations, binding stoichiometry, DNA melting experiments, as well as viscosity measurement. The results indicate that complexes 1 and 2 bind to DNA via the interaction of the planar π-delocalized system of the complexes with intrinsic binding constants of 4.18 × 10^5 and 3.85 × 10^6 L/tool, respectively, and non-electrostatic binding free energy makes a predominant contribution to the binding free energy. The in vitro cytotoxic activity of complexes 1 and 2 was evaluated by the MTT[3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyl- 2H-tetrazolium bromide] method. Complex I shows higher anticancer potency than complex 2 against four tumor cell lines. Further mechanism study indicates that complexes 1 and 2 can cause cell cycle arrest in the G2/M phase.
文摘13C and 99Ru-NMR chendcal shifts are reported for the ruthenium(II) tris complexes of5-substitUted 1,10-phenanthrolines. It has been found that both of them are affected by the substituents on the phenanthrolines in a direction consistent with that expected from the electron withdrawing ability of the substituent.
文摘The two mixed ligand complexes, cis [Ru(mnt)(bpy)2] (1) and cis [Ru (dmit)(bpy)2] (2) (where mnt2- is maleonitriledithiolate and dmit2- reprents 4,5 dimercapto 1,3 dithiole 2 thione), have been synthesized and characterized by element analysis and IR spectra. The electronic spectra of 1 and 2 in DMF solutions showed that the two complexes have broad absorption charge transfer bands [LMCT i.e. charge transfer from dithiolate to Ru? or LL′CT, that is, charge transfer from dithiolate to 2,2′ bipyridine] in the visible region. Compared with 1, the LMCT or LL′CT band for 2 shifts to low frequency. The results of electrochemistry of the two complexes in DMF are consistent with that of the electronic spectra.
