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
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
Two new Gd Ⅲ complexes with nitrilotriacetic acid(nta) and trans-1,2-cyclohexanediaminetetraacetic acid(Cydta) ligands were synthesized. Their crystal structures were determined by single-crystal X-ray structure anal...Two new Gd Ⅲ complexes with nitrilotriacetic acid(nta) and trans-1,2-cyclohexanediaminetetraacetic acid(Cydta) ligands were synthesized. Their crystal structures were determined by single-crystal X-ray structure analyses. The crystal data are as follows: K 3[Gd Ⅲ(nta) 2·(H 2O)]·6H 2O, monoclinic system, C2/c space group, a=1.534 81(15) nm, b=1.292 05(12) nm, c=2.610 8(3) nm, β=96.244(2)°, V=5.146 7(9) nm 3, Z=8, M=776.87, D c=2.005 g/cm 3, μ= 3.149 mm -1 and \{F(000)=\}3 080, R=0.024 5, wR=0.064 3 for 4 455 unique reflections and R= 0.028 9, wR=0.067 2 for all 10 305 reflections. The Gd ⅢN 2O 7 part in the [Gd Ⅲ(nta) 2(H 2O)] 3- anion is a pseudo-monocapped square antiprismatic nine-coordination structure.(NH 4)[Gd Ⅲ(Cydta)(H 2O) 2]·5H 2O, triclinic system, P1 space group, a=0.866 2(3) nm, b=1.006 7(3) nm, c= 1.444 8(5) nm, α= 88.282(5)°, β=75\^190(5)°, γ=88.317(4)°, V=1.217 2(7) nm 3, Z=2, M=643.69, D c=1.756 g/cm 3, μ=2.798 mm -1 and F(000)=650, R=0.030 3, wR=0.080 9 for 4 273 unique reflections and R=0.033 2, wR=0.082 5 for all 5 062 reflections. The Gd ⅢN 2O 6 part in the [Gd Ⅲ(Cydta)(H 2O) 2] - anion has a pseudo-square antiprismatic eight-coordination structure.展开更多
Diethylenetriaminepentaacetic dianhydride was co-polymerized with dodecyl ester and benzyl ester of lysine,and octodecyl ester and benzyl ester of lysine respectively to give two terpolymers. These two terpolymer liga...Diethylenetriaminepentaacetic dianhydride was co-polymerized with dodecyl ester and benzyl ester of lysine,and octodecyl ester and benzyl ester of lysine respectively to give two terpolymers. These two terpolymer ligands were reacted with GdCl 3 to afford amphiphilic oligomers of Gd(Ⅲ) complexes. These new ligands and Gd(Ⅲ) complexes were characterized by IR, 1H NMR and elemental analysis. The oligomeric complexes show a higher relaxivity as compared to that of Gd(DTPA) which is widely used in clinic diagnoses. The Gd(Ⅲ) complex derived from octodecyl ester demonstrated liver-selective enhancement for MR imaging of Wistar rat. The ratios of signal to noise ( S/N ) in the proton intensity imaging were enhanced,respectively,by 15%,27%,and 36% at the time of 5,30 and 45 min after injection of this complex.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
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.
文摘Two new Gd Ⅲ complexes with nitrilotriacetic acid(nta) and trans-1,2-cyclohexanediaminetetraacetic acid(Cydta) ligands were synthesized. Their crystal structures were determined by single-crystal X-ray structure analyses. The crystal data are as follows: K 3[Gd Ⅲ(nta) 2·(H 2O)]·6H 2O, monoclinic system, C2/c space group, a=1.534 81(15) nm, b=1.292 05(12) nm, c=2.610 8(3) nm, β=96.244(2)°, V=5.146 7(9) nm 3, Z=8, M=776.87, D c=2.005 g/cm 3, μ= 3.149 mm -1 and \{F(000)=\}3 080, R=0.024 5, wR=0.064 3 for 4 455 unique reflections and R= 0.028 9, wR=0.067 2 for all 10 305 reflections. The Gd ⅢN 2O 7 part in the [Gd Ⅲ(nta) 2(H 2O)] 3- anion is a pseudo-monocapped square antiprismatic nine-coordination structure.(NH 4)[Gd Ⅲ(Cydta)(H 2O) 2]·5H 2O, triclinic system, P1 space group, a=0.866 2(3) nm, b=1.006 7(3) nm, c= 1.444 8(5) nm, α= 88.282(5)°, β=75\^190(5)°, γ=88.317(4)°, V=1.217 2(7) nm 3, Z=2, M=643.69, D c=1.756 g/cm 3, μ=2.798 mm -1 and F(000)=650, R=0.030 3, wR=0.080 9 for 4 273 unique reflections and R=0.033 2, wR=0.082 5 for all 5 062 reflections. The Gd ⅢN 2O 6 part in the [Gd Ⅲ(Cydta)(H 2O) 2] - anion has a pseudo-square antiprismatic eight-coordination structure.
文摘Diethylenetriaminepentaacetic dianhydride was co-polymerized with dodecyl ester and benzyl ester of lysine,and octodecyl ester and benzyl ester of lysine respectively to give two terpolymers. These two terpolymer ligands were reacted with GdCl 3 to afford amphiphilic oligomers of Gd(Ⅲ) complexes. These new ligands and Gd(Ⅲ) complexes were characterized by IR, 1H NMR and elemental analysis. The oligomeric complexes show a higher relaxivity as compared to that of Gd(DTPA) which is widely used in clinic diagnoses. The Gd(Ⅲ) complex derived from octodecyl ester demonstrated liver-selective enhancement for MR imaging of Wistar rat. The ratios of signal to noise ( S/N ) in the proton intensity imaging were enhanced,respectively,by 15%,27%,and 36% at the time of 5,30 and 45 min after injection of this complex.
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.
