The interaction of metal ions（Hg^2＋,Pb^2＋,Co^2＋,Mn^2＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ） was investigated,and four new complexes ...The interaction of metal ions（Hg^2＋,Pb^2＋,Co^2＋,Mn^2＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ） was investigated,and four new complexes have been synthesized and characterized.Complex 1 exhibits a 0dimensional dual-core structure,2 is a one-dimensional chain structure based on a dual-core Pb unit,while 3 and 4 show a 0 dimensional single-core structural unit.Complex 1 is of monoclinic system,space group C2/c with a = 19.211（4）,b = 23.896（5）,c = 12.698（3） A°,β= 120.11（3）°,V= 5043.0（17）A°3,Z = 4,S = 1.053,F（000） = 2976,R^a = 0.0637 and wR^b = 0.1068（I 〉 2σ（I））.Complex 2 adopts triclinic system,space group P1 with a = 10.370（2）,b = 12.195（2）,c = 21.033（4） A°,α = 80.87（3）,β= 81.22（3）,γ = 82.38（3）°,V= 2579.3（8） A°3,Z = 2,S = 1.099,F（000） = 1328,R^a = 0.0609 and wR^b =0.1365（I 〉 2σ（I））.Complex 3 is of monoclinic system,space group Cllc with a = 14.166（3）,b =16.621（3）,c = 20.248（4） ？,β = 92.18（3）°,V= 4764.0（16） A°3,Z = 4,S = 1.005,F（000） = 2108,R^a =0.0589 and wR^b = 0.1332（I 〉 2σ（I））.Complex 4 belongs to the monoclinic system,space group C2/c with a = 14.404（3）,b = 16.626（3）,c = 20.346（4） ？,β = 92.43（3）°,V= 4868.2（17） A°3,Z = 4,S= 1.068,F（000） = 2108,R^a = 0.0833 and wR^b = 0.1591（I 〉 2σ（I））.Furthermore,the behavior of HPDQ with Hg^2＋,Pb^2＋,Co^2＋ and Mn^2＋ in the solution was also investigated,and the result shows after the metal ions were added respectively,the emission of all solutions shows fluorescence quenching and has a red shift compared with that of the HPDQ ligand.展开更多
Photoinduced electron transfer reaction between the excited state ruthenium (II) polypyridyl complexes and quinones has been investigated in cetyltrimethylammonium bromide using luminescent quenching techniques. The c...Photoinduced electron transfer reaction between the excited state ruthenium (II) polypyridyl complexes and quinones has been investigated in cetyltrimethylammonium bromide using luminescent quenching techniques. The complexes have the absorption and emission maximum in the range 452 - 468 nm and 594 - 617 nm respectively. The static nature of quenching is confirmed from the ground state absorption studies. The association constants for the complexes with quinones are calculated from the Benesi-Hildebrand plots using absorption spectral data. The value of quenching rate constant (kq) is highly sensitive to the nature of the ligand and the quencher, the medium, structure and size of the quenchers. Compared to the aqueous medium, the electron transfer rate is altered in CTAB medium. The oxidative nature of the quenching is confirmed by the formation of Ru3+ ion and quinone anion radical.展开更多
Two high coordination crystals were obtained by the interaction of Ce^（3＋） and Nd^（3＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ）, and the...Two high coordination crystals were obtained by the interaction of Ce^（3＋） and Nd^（3＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ）, and they were characterized. Complex 1 exhibits a 0 dimensional three-nuclear structure, with the three Ce（Ⅲ） atoms being ten-, eleven- and twelve-coordinated. Complex 2 is a 0 dimensional dual-core structure and the Nd（Ⅲ） atom is ten-coordinated. Complex 1 is of monoclinic system, space group P2/c with a = 16.850（3）, b = 16.617（3）, c = 24.017（5） ？, β = 100.94（3）o, V = 6602（2） ？~3, Z = 4, S = 1.062, F（000） = 3372, R = 0.0504 and wR = 0.1463（I 〉 2σ（I））. Complex 2 adopts a monoclinic system, space group C2/c with a = 25.795（5）, b = 20.166（4）, c = 13.059（3） ？, β = 112.29（3）°, V = 6286（2） ？~3, Z = 4, S = 1.004, F（000） = 2664, R = 0.0663 and wR = 0.1821（I 〉 2σ（I））. Furthermore, the behaviors of HPDQ with Ce^（3＋） and Nd^（3＋） in the solution are also investigated. After the Ce^（3＋） is added, the ultraviolet absorption of the solution is enhanced with a red shift compared with that of the HPDQ ligand. While after adding Nd^（3＋）, the ultraviolet absorption of the solution is weakened, and it has a red shift which is the same as Ce^（3＋）. However, after the respective addition of metal ions, the emission of all solutions is quenched and has a red shift compared with that of the HPDQ ligand.展开更多
In photodynamic therapy(PDT),Ru(Ⅱ)polypyridyl complexes(RPCs)featuring the popularπ-expansive benzo[i]dipyrido[3,2-a:2’,3’-c]phenazine(dppn)ligand have attracted much attention,mainly due to the good singlet oxyge...In photodynamic therapy(PDT),Ru(Ⅱ)polypyridyl complexes(RPCs)featuring the popularπ-expansive benzo[i]dipyrido[3,2-a:2’,3’-c]phenazine(dppn)ligand have attracted much attention,mainly due to the good singlet oxygen sensitizing properties imparted by this peculiar ligand.However,notwithstanding the intriguing perspectives,much remains to be explored about the use of RPC-based photosensitizing agents(PSs)with more than a dppn ligand in their scaffolds.展开更多
Ruthenium polypyridyl complexes are known for their excellent photophysical properties and rich electrochemical behavior.Thus,developing complexes with multifunctional behavior showing potential applications in multip...Ruthenium polypyridyl complexes are known for their excellent photophysical properties and rich electrochemical behavior.Thus,developing complexes with multifunctional behavior showing potential applications in multiple fields is of great importance.Herein,we report a new aggregation-induced emission(AIE)active bis-heteroleptic ruthenium(Ⅱ)complex(Ru-4)of 4,7-diamino 1,10-phenanthroline along with a series of other bis-heteroleptic Ru(Ⅱ)polypyridyl complexes(Ru-1,Ru-2 and Ru-3)containing 4,7-disubstituted 1,10-phenanthroline and two homoleptic complexes(Ru-5 and Ru-6)of 2,2’-bipyridine and 1,10-phenanthroline.展开更多
A new generation series of cyclometalated Ru(Ⅱ)polypyridyl complexes of the type[Ru(C^N)(N^N)_(2)]^(+),Ru1–Ru4,were rationally designed and synthesized,where N^N=2,2’-bipyridine(bpy)and dipyrido[3,2-d:2’,3’-f]qui...A new generation series of cyclometalated Ru(Ⅱ)polypyridyl complexes of the type[Ru(C^N)(N^N)_(2)]^(+),Ru1–Ru4,were rationally designed and synthesized,where N^N=2,2’-bipyridine(bpy)and dipyrido[3,2-d:2’,3’-f]quinoxaline(dpq)and C^N=deprotonated methyl 1-butyl-2-aryl-benzimidazolecarboxylate with p-CF_(3)C_(6)H_(4)or p-Me_(2)NC_(6)H_(4)substituents in the R3 position of the phenyl ring.The photophysical properties of Ru1–Ru4 revealed absorption maxima around 560 nm with an absorption up to 700 nm.The new Ru complexes were able to generate singlet oxygen(^(1)O_(2))upon green light irradiation in acetonitrile,with complexes containing the CF_(3)group,Ru1 and Ru3,being the best performers.Furthermore,Ru1 and Ru3 were also able to photogenerate hydroxyl radicals OH•.By having PSs capable of undergoing both typeⅠand typeⅡmechanisms,a broader range of cytotoxic effects is achieved.Ru1–Ru4 accumulated in membrane-rich compartments,including the cytoplasmic membrane,mitochondria,and endoplasmic reticulum in HeLa cells.Upon irradiation of Ru1 with green light,all these compartments were damaged in treated cells.Based on in vitro experiments,we deduced that the compound Ru1 under irradiation has the capability to disrupt phospholipid membranes directly.Additionally,differential scanning calorimetry of living cells also indicated damage of cytoplasmic/membrane proteins,ultimately leading to cell death via oncosis.展开更多
Direct photoreduction of CO_(2)from flue gas is an energy-saving avenue to realize the carbon-neutral cycle but it is still in its infancy.Herein,we constructed a new anionic metal-organic framework based on trinuclea...Direct photoreduction of CO_(2)from flue gas is an energy-saving avenue to realize the carbon-neutral cycle but it is still in its infancy.Herein,we constructed a new anionic metal-organic framework based on trinuclear Ni clusters and thiophenecarboxylic acid for CO_(2)photoreduction of exhaust gas from a power plant.Under visible-light irradiation,the yield of CO was 17.4-26.3 mmol g^(-1)in diluted CO_(2)with a concentration of 5-20%.The apparent quantum yield(A.Q.Y.)under a 10%CO_(2)atmosphere was determined to be 2.1%,which ranks among the highest values of the reported photocatalysts under similar conditions.Importantly,in real flue gas containing 10%CO_(2),a selectivity of 90.4%was achieved and CO generation reached 18.2 mmol g^(-1).In situ transient photovoltage(TPV)and density functional theory(DFT)calculations showed that the formation of a CO_(2)bridged photocatalytic interface between Ni-MOF1 and a Ru complex([Ru(bpy)_(3)]Cl_(2)/[Ru(bpy)_(2)]Cl_(2))was a crucial factor for the efficient CO_(2)-to-CO conversion in diluted CO_(2).展开更多
There is considerable research interest and vigorous debate about the DNA binding of polypyridyl complexes including the electron transfer involving DNA. In this review, based on the fluorescence quenching experiments...There is considerable research interest and vigorous debate about the DNA binding of polypyridyl complexes including the electron transfer involving DNA. In this review, based on the fluorescence quenching experiments, it was proposed that DNA might serve as a conductor. From the time-interval CD spectra, the different binding rates of Δ- and Λ-enantiomer to calf thymus DNA were observed. The factors influencing the DNA-binding of polypyridyl complexes, and the potential bio-functions of the complexes are also discussed.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
A novel complex [Co(phen)2HPlP]Cl3[phen= phenanethroline, HPIP=2-(2-hydroxyphenyl) imidazo [4,5-f][l,10]phenanethroline] has been synthesized and structurally characterized by elemental analysis, UV, IR and 1H NMR spe...A novel complex [Co(phen)2HPlP]Cl3[phen= phenanethroline, HPIP=2-(2-hydroxyphenyl) imidazo [4,5-f][l,10]phenanethroline] has been synthesized and structurally characterized by elemental analysis, UV, IR and 1H NMR spectroscopies. The interaction of the complex with calf thymus DNA (CT DNA) has been studied using absorption and emission spectroscopy, DNA melting techniques and cyclic voltammetry. The compound shows absorption hypochromicity, fluorescence enhancement and DNA melting temperature increment when binding to CT DNA. CV measurement shows a shift in reduction potential and a change in peak current with addition of DNA. These results prove mat the compound inserts into DNA base pairs. The shift of peak potential indicates the ion interaction mode between the complex and DNA. The binding constant of the compound to DNA is 4.37 × 104. The complex also seems to be an efficient photocleavage reagent.展开更多
Two polypyridyl ligands DCHIP (2 hydro 3,5 dichlorophenyl imidazo phenanthroline),MDHIP(2,4 dihydrophenyl imidazophenanthroline) and their ruthenium?complexes [Ru(phen)2 MDHIP]2+and [Ru(phen)2DCHIP]2+were prepared. Th...Two polypyridyl ligands DCHIP (2 hydro 3,5 dichlorophenyl imidazo phenanthroline),MDHIP(2,4 dihydrophenyl imidazophenanthroline) and their ruthenium?complexes [Ru(phen)2 MDHIP]2+and [Ru(phen)2DCHIP]2+were prepared. Their DNA binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the complexes both bound to DNA by partial intercalation mode, but [Ru(phen)2DCHIP]2+exhibited stronger binding affinity for DNA than [Ru(phen)2 MDHIP]2+due to the different planarities and steric effects of ligands. On the other hand, after binding to DNA, the fluorescence intensity of [Ru(phen)2MDHIP]2+decreased, while the fluorescence intensity of [Ru(phen)2 DCHIP]2+increased.展开更多
Two structurally related polypyridyl ligands ODHIP(3,4-dihydroxyl-imidazophenanthroline), MDHIP(2,4-dihydroxyl-imidazo phenanthroline) and their ruthenium(II) complexes [Ru(phen) 2ODHIP] 2+ and [Ru(phen) 2MDHIP] 2+ we...Two structurally related polypyridyl ligands ODHIP(3,4-dihydroxyl-imidazophenanthroline), MDHIP(2,4-dihydroxyl-imidazo phenanthroline) and their ruthenium(II) complexes [Ru(phen) 2ODHIP] 2+ and [Ru(phen) 2MDHIP] 2+ were prepared and characterized. Their DNA-binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the two complexes are bound to DNA by different modes due to the different planarities of ligands. For the complex [Ru(phen) 2MDHIP] 2+, the 2- position ortho group of MDHIP could form an intramolecular hydrogen bond with the nitrogen atom of the imidazole ring to extend the planarity and strengthen the binding affinity. On the other hand, the 4- position ortho group hindered the complex from intercalating into the base pairs of DNA, and finally, making the complex bind to DNA by a partial intercalative mode. However, for the complex [Ru(phen) 2ODHIP] 2+, there was no intramolecular hydrogen bond formed and the two ortho groups further increased the steric effect and decreased the binding affinity, thus making the complex bind to DNA by groove binding mode.展开更多
基金supported by the NNSFC(21301100)the Education Department Fund of Henan(13A150819)Special fund of Nanyang Normal University(ZX2013029)
文摘The interaction of metal ions（Hg^2＋,Pb^2＋,Co^2＋,Mn^2＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ） was investigated,and four new complexes have been synthesized and characterized.Complex 1 exhibits a 0dimensional dual-core structure,2 is a one-dimensional chain structure based on a dual-core Pb unit,while 3 and 4 show a 0 dimensional single-core structural unit.Complex 1 is of monoclinic system,space group C2/c with a = 19.211（4）,b = 23.896（5）,c = 12.698（3） A°,β= 120.11（3）°,V= 5043.0（17）A°3,Z = 4,S = 1.053,F（000） = 2976,R^a = 0.0637 and wR^b = 0.1068（I 〉 2σ（I））.Complex 2 adopts triclinic system,space group P1 with a = 10.370（2）,b = 12.195（2）,c = 21.033（4） A°,α = 80.87（3）,β= 81.22（3）,γ = 82.38（3）°,V= 2579.3（8） A°3,Z = 2,S = 1.099,F（000） = 1328,R^a = 0.0609 and wR^b =0.1365（I 〉 2σ（I））.Complex 3 is of monoclinic system,space group Cllc with a = 14.166（3）,b =16.621（3）,c = 20.248（4） ？,β = 92.18（3）°,V= 4764.0（16） A°3,Z = 4,S = 1.005,F（000） = 2108,R^a =0.0589 and wR^b = 0.1332（I 〉 2σ（I））.Complex 4 belongs to the monoclinic system,space group C2/c with a = 14.404（3）,b = 16.626（3）,c = 20.346（4） ？,β = 92.43（3）°,V= 4868.2（17） A°3,Z = 4,S= 1.068,F（000） = 2108,R^a = 0.0833 and wR^b = 0.1591（I 〉 2σ（I））.Furthermore,the behavior of HPDQ with Hg^2＋,Pb^2＋,Co^2＋ and Mn^2＋ in the solution was also investigated,and the result shows after the metal ions were added respectively,the emission of all solutions shows fluorescence quenching and has a red shift compared with that of the HPDQ ligand.
文摘Photoinduced electron transfer reaction between the excited state ruthenium (II) polypyridyl complexes and quinones has been investigated in cetyltrimethylammonium bromide using luminescent quenching techniques. The complexes have the absorption and emission maximum in the range 452 - 468 nm and 594 - 617 nm respectively. The static nature of quenching is confirmed from the ground state absorption studies. The association constants for the complexes with quinones are calculated from the Benesi-Hildebrand plots using absorption spectral data. The value of quenching rate constant (kq) is highly sensitive to the nature of the ligand and the quencher, the medium, structure and size of the quenchers. Compared to the aqueous medium, the electron transfer rate is altered in CTAB medium. The oxidative nature of the quenching is confirmed by the formation of Ru3+ ion and quinone anion radical.
基金supported by the NNSFC(21301100)the Education Department Fund of Henan(13A150819)Special fund of Nanyang Normal University(ZX2013029)
文摘Two high coordination crystals were obtained by the interaction of Ce^（3＋） and Nd^（3＋） with polypyridyl quinoxaline ligand 2,3,6,7,10,11-hexakis（2-pyridyl）dipyrazino[2,3-f：20,30-h]quinoxaline（HPDQ）, and they were characterized. Complex 1 exhibits a 0 dimensional three-nuclear structure, with the three Ce（Ⅲ） atoms being ten-, eleven- and twelve-coordinated. Complex 2 is a 0 dimensional dual-core structure and the Nd（Ⅲ） atom is ten-coordinated. Complex 1 is of monoclinic system, space group P2/c with a = 16.850（3）, b = 16.617（3）, c = 24.017（5） ？, β = 100.94（3）o, V = 6602（2） ？~3, Z = 4, S = 1.062, F（000） = 3372, R = 0.0504 and wR = 0.1463（I 〉 2σ（I））. Complex 2 adopts a monoclinic system, space group C2/c with a = 25.795（5）, b = 20.166（4）, c = 13.059（3） ？, β = 112.29（3）°, V = 6286（2） ？~3, Z = 4, S = 1.004, F（000） = 2664, R = 0.0663 and wR = 0.1821（I 〉 2σ（I））. Furthermore, the behaviors of HPDQ with Ce^（3＋） and Nd^（3＋） in the solution are also investigated. After the Ce^（3＋） is added, the ultraviolet absorption of the solution is enhanced with a red shift compared with that of the HPDQ ligand. While after adding Nd^（3＋）, the ultraviolet absorption of the solution is weakened, and it has a red shift which is the same as Ce^（3＋）. However, after the respective addition of metal ions, the emission of all solutions is quenched and has a red shift compared with that of the HPDQ ligand.
基金Department of Chemistry Ugo Schiff of the University of Florence for the Cryo-TEM measurements.UniCA-Progetti biennali di Ateno Finanziati dalla Fondazione di Sardegna 2018(CUP F741I19000950007)is gratefully acknowledged for(partial)financial support.
文摘In photodynamic therapy(PDT),Ru(Ⅱ)polypyridyl complexes(RPCs)featuring the popularπ-expansive benzo[i]dipyrido[3,2-a:2’,3’-c]phenazine(dppn)ligand have attracted much attention,mainly due to the good singlet oxygen sensitizing properties imparted by this peculiar ligand.However,notwithstanding the intriguing perspectives,much remains to be explored about the use of RPC-based photosensitizing agents(PSs)with more than a dppn ligand in their scaffolds.
文摘Ruthenium polypyridyl complexes are known for their excellent photophysical properties and rich electrochemical behavior.Thus,developing complexes with multifunctional behavior showing potential applications in multiple fields is of great importance.Herein,we report a new aggregation-induced emission(AIE)active bis-heteroleptic ruthenium(Ⅱ)complex(Ru-4)of 4,7-diamino 1,10-phenanthroline along with a series of other bis-heteroleptic Ru(Ⅱ)polypyridyl complexes(Ru-1,Ru-2 and Ru-3)containing 4,7-disubstituted 1,10-phenanthroline and two homoleptic complexes(Ru-5 and Ru-6)of 2,2’-bipyridine and 1,10-phenanthroline.
基金supported by the Czech Science Foundation(grant 23-06316S)supported by the Spanish Ministerio de Ciencia e Innovación-Agencia Estatal de Investigación(MCI/AEI/10.13039/501100011033)+2 种基金FEDER funds(project PID2021-122850NB-I00)Fundación Séneca-CARM(project 21989/PI/22)Fundación Séneca-CARM for a grant(project 21426/FPI/20).
文摘A new generation series of cyclometalated Ru(Ⅱ)polypyridyl complexes of the type[Ru(C^N)(N^N)_(2)]^(+),Ru1–Ru4,were rationally designed and synthesized,where N^N=2,2’-bipyridine(bpy)and dipyrido[3,2-d:2’,3’-f]quinoxaline(dpq)and C^N=deprotonated methyl 1-butyl-2-aryl-benzimidazolecarboxylate with p-CF_(3)C_(6)H_(4)or p-Me_(2)NC_(6)H_(4)substituents in the R3 position of the phenyl ring.The photophysical properties of Ru1–Ru4 revealed absorption maxima around 560 nm with an absorption up to 700 nm.The new Ru complexes were able to generate singlet oxygen(^(1)O_(2))upon green light irradiation in acetonitrile,with complexes containing the CF_(3)group,Ru1 and Ru3,being the best performers.Furthermore,Ru1 and Ru3 were also able to photogenerate hydroxyl radicals OH•.By having PSs capable of undergoing both typeⅠand typeⅡmechanisms,a broader range of cytotoxic effects is achieved.Ru1–Ru4 accumulated in membrane-rich compartments,including the cytoplasmic membrane,mitochondria,and endoplasmic reticulum in HeLa cells.Upon irradiation of Ru1 with green light,all these compartments were damaged in treated cells.Based on in vitro experiments,we deduced that the compound Ru1 under irradiation has the capability to disrupt phospholipid membranes directly.Additionally,differential scanning calorimetry of living cells also indicated damage of cytoplasmic/membrane proteins,ultimately leading to cell death via oncosis.
基金National Natural Science Foundation of China(21971032 and 22175033)the Education Department of Jilin Province(JJKH20221153KJ).
文摘Direct photoreduction of CO_(2)from flue gas is an energy-saving avenue to realize the carbon-neutral cycle but it is still in its infancy.Herein,we constructed a new anionic metal-organic framework based on trinuclear Ni clusters and thiophenecarboxylic acid for CO_(2)photoreduction of exhaust gas from a power plant.Under visible-light irradiation,the yield of CO was 17.4-26.3 mmol g^(-1)in diluted CO_(2)with a concentration of 5-20%.The apparent quantum yield(A.Q.Y.)under a 10%CO_(2)atmosphere was determined to be 2.1%,which ranks among the highest values of the reported photocatalysts under similar conditions.Importantly,in real flue gas containing 10%CO_(2),a selectivity of 90.4%was achieved and CO generation reached 18.2 mmol g^(-1).In situ transient photovoltage(TPV)and density functional theory(DFT)calculations showed that the formation of a CO_(2)bridged photocatalytic interface between Ni-MOF1 and a Ru complex([Ru(bpy)_(3)]Cl_(2)/[Ru(bpy)_(2)]Cl_(2))was a crucial factor for the efficient CO_(2)-to-CO conversion in diluted CO_(2).
基金Acknowledgements We are grateful to the State Key Laboratory of Coordination Chemistry in Nanjing University, the State Key Laboratory of Bio-organic and Natural Products Chemistry in Shanghai Institute of Organic Chemistry for their financial support. T
文摘There is considerable research interest and vigorous debate about the DNA binding of polypyridyl complexes including the electron transfer involving DNA. In this review, based on the fluorescence quenching experiments, it was proposed that DNA might serve as a conductor. From the time-interval CD spectra, the different binding rates of Δ- and Λ-enantiomer to calf thymus DNA were observed. The factors influencing the DNA-binding of polypyridyl complexes, and the potential bio-functions of the complexes are also discussed.
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theNationalNaturalScienceFoundationofChina (No .2 0 1710 31)andtheNaturalScienceFoundationofShanxiProvince (No .2 0 0 110 0 7)
文摘A novel complex [Co(phen)2HPlP]Cl3[phen= phenanethroline, HPIP=2-(2-hydroxyphenyl) imidazo [4,5-f][l,10]phenanethroline] has been synthesized and structurally characterized by elemental analysis, UV, IR and 1H NMR spectroscopies. The interaction of the complex with calf thymus DNA (CT DNA) has been studied using absorption and emission spectroscopy, DNA melting techniques and cyclic voltammetry. The compound shows absorption hypochromicity, fluorescence enhancement and DNA melting temperature increment when binding to CT DNA. CV measurement shows a shift in reduction potential and a change in peak current with addition of DNA. These results prove mat the compound inserts into DNA base pairs. The shift of peak potential indicates the ion interaction mode between the complex and DNA. The binding constant of the compound to DNA is 4.37 × 104. The complex also seems to be an efficient photocleavage reagent.
文摘Two polypyridyl ligands DCHIP (2 hydro 3,5 dichlorophenyl imidazo phenanthroline),MDHIP(2,4 dihydrophenyl imidazophenanthroline) and their ruthenium?complexes [Ru(phen)2 MDHIP]2+and [Ru(phen)2DCHIP]2+were prepared. Their DNA binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the complexes both bound to DNA by partial intercalation mode, but [Ru(phen)2DCHIP]2+exhibited stronger binding affinity for DNA than [Ru(phen)2 MDHIP]2+due to the different planarities and steric effects of ligands. On the other hand, after binding to DNA, the fluorescence intensity of [Ru(phen)2MDHIP]2+decreased, while the fluorescence intensity of [Ru(phen)2 DCHIP]2+increased.
文摘Two structurally related polypyridyl ligands ODHIP(3,4-dihydroxyl-imidazophenanthroline), MDHIP(2,4-dihydroxyl-imidazo phenanthroline) and their ruthenium(II) complexes [Ru(phen) 2ODHIP] 2+ and [Ru(phen) 2MDHIP] 2+ were prepared and characterized. Their DNA-binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the two complexes are bound to DNA by different modes due to the different planarities of ligands. For the complex [Ru(phen) 2MDHIP] 2+, the 2- position ortho group of MDHIP could form an intramolecular hydrogen bond with the nitrogen atom of the imidazole ring to extend the planarity and strengthen the binding affinity. On the other hand, the 4- position ortho group hindered the complex from intercalating into the base pairs of DNA, and finally, making the complex bind to DNA by a partial intercalative mode. However, for the complex [Ru(phen) 2ODHIP] 2+, there was no intramolecular hydrogen bond formed and the two ortho groups further increased the steric effect and decreased the binding affinity, thus making the complex bind to DNA by groove binding mode.
