A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.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
Carbon dot(CD)is an edge-bound,nanometer-sized carbon material possessing unique optical and electronic properties,making it promising metal-free,environmentally benign.In this study,we identified a highly hydrophilic...Carbon dot(CD)is an edge-bound,nanometer-sized carbon material possessing unique optical and electronic properties,making it promising metal-free,environmentally benign.In this study,we identified a highly hydrophilic CD complexed with Fe(Ⅲ)via carboxyl groups to form CD-COOFeⅢ,which exhibited remarkably enhanced Fenton-like reaction performance boosted by visible light irradiation.CD-COOFeⅢenabled high activity in the visible region beyondλ>420 nm,and maintained stable oxidation efficiency in the presence of H_(2)O_(2)over at least ten cycles.The capacity of electrons transferred from photo-excited CD to reduce Fe(Ⅲ)was calculated to be 1.1 mmol/g of CD.Furthermore,the quantum yield(QY)of solarto-Fe(Ⅱ)conversion reached an impressive 87.7%.These findings not only suggest a viable strategy for efficient conversion of solar-to-chemical using a CD-COOFeⅢcomplex in visible light boosted Fenton-like oxidation reaction,but also provide insight for understanding the effect of nanosized artificial and/or natural carbon materials in iron recycling in a natural surface environment.展开更多
The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The...The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).展开更多
A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.95...A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.展开更多
The luminescent rare earth(RE)complex based multifunctional nanocomposites offer new potential applications of multimodal imaging(magnetic resonance imaging(MRI),fluorescent bioimaging,etc.)that can be associated with...The luminescent rare earth(RE)complex based multifunctional nanocomposites offer new potential applications of multimodal imaging(magnetic resonance imaging(MRI),fluorescent bioimaging,etc.)that can be associated with therapeutic activities.In this study,we report some results obtained with novel multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites that are composed of europium(Ⅲ)complex with 1-(2-naphthoyl)-3,3,3-trifluoroacetone ligands(NTA)(Eu(NTA)3)and superparamagnetic Fe3O4 nanoparticles.These nanocomposites were functionalized with an amine group for biomedicine application.The multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites exhibit both good magnetic behavior of Fe3O4 nanoparticles as a core and strong fluorescent property of europium(Ⅲ)complex.Their characterizations were analyzed by XRD,SEM,EDX and FTIR spectra.The optical properties were studied in detail by UV-VIS spectra and luminescent emission spectra.The magnetic property was estimated by VMS.The effect of concentrations of luminescent Eu(NTA)3 complex on luminescent and magnetic properties is discussed.展开更多
A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elem...A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].展开更多
A new europium(Ⅲ)complex Eu_(2)(C_(15)H_(11)O_(3))_(6)(C_(12)H_(8)N_(2))_(2)has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:mon...A new europium(Ⅲ)complex Eu_(2)(C_(15)H_(11)O_(3))_(6)(C_(12)H_(8)N_(2))_(2)has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_(1/n),a=15.1238(5),b=13.5928(4),c=22.9840(7)A,β=104.132(3)o,V=4582.0(2)A3,Dc=1.522 g/cm^(3),Z=4,μ(Mo Kα)=1.433 mm^(-1),F(000)=2128,the final R=0.0447 and wR=0.0826.The Eu(Ⅲ)ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu^(3+):5 D0→7 F1(594 nm)and 5 D0→7 F2(617 nm).The complex is an antiferromagnetism system in the range of 150~300 K.Also reported in the paper is the thermal stability property of the title complex.展开更多
Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we de...Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.展开更多
Two complexes[Ni(L)(OAc)](1)and[Co(L)2]Cl·4CH3OH(2)(HL=2-aceto-3-methylpyrazine N-(4-fluorophenyl)thiosemicarbazone)have been synthesized and structurally determined by single-crystal X-ray diffraction,elemental ...Two complexes[Ni(L)(OAc)](1)and[Co(L)2]Cl·4CH3OH(2)(HL=2-aceto-3-methylpyrazine N-(4-fluorophenyl)thiosemicarbazone)have been synthesized and structurally determined by single-crystal X-ray diffraction,elemental analysis and IR spectroscopy.X-ray diffraction analysis results show that the Ni(Ⅱ)ion in complex 1 with a distorted square planar geometry is surrounded by one anionic TSC ligand with NNS donor set and one monodentate acetate.By contrast,Co(Ⅲ)ion coordinates with two tridentate TSC ligands,and thus possessing a distorted octahedron coordination geometry.Moreover,the fluorescence spectra indicate that the interactions of complexes 1 and 2 with DNA are stronger than that of the ligand HL.CCDC:1848437,1;1848438,2.展开更多
The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine o...The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...展开更多
Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of...Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.展开更多
A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysi...A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090（2）, b = 8.0824（13）, c = 15.5591（17） ?, V = 1775.4（5） ?3, Mr = 576.22, Dc = 2.156 g/cm3, μ（Mo Kα） = 4.059 mm-1, F（000） = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections（I > 2σ（I））. Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium（Ⅲ） ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.展开更多
A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these c...A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.展开更多
A complex of terbium(Ⅲ) with Schiff base salicylaldehyde-taurine and 1,10-phenanthroline was synthesized. The molecular formula was [Tb (sal-taurine) (1,10-phen) (NO_3)]·2H_2O (sal=salicylaldehyde, 1,10-phen=1,1...A complex of terbium(Ⅲ) with Schiff base salicylaldehyde-taurine and 1,10-phenanthroline was synthesized. The molecular formula was [Tb (sal-taurine) (1,10-phen) (NO_3)]·2H_2O (sal=salicylaldehyde, 1,10-phen=1,10-phenanthroline). The composition of the title complex was determined by elemental analysis and EDTA volumetic analysis. IR, Molar conductivity and X-ray powder diffraction were performed for its characterizations. The thermal decomposition kinetics of the complex were investigated under non-isothermal condition using the Achar differential method and the Coats-Redfern integral method. The kinetic equation for the second step corresponds to the mechanisms of the Zhuralev, Lesokin and Templman equation were obtained.展开更多
A new cucurbit[6]uril bridsed binuclear complex {[Gd（H2O）6]2[Q6（H2O）]}C16·4H2O, where Q6 represents cucurbit[6]uril, has been synthesized and characterized by X-ray diffraction. The crystal structure shows th...A new cucurbit[6]uril bridsed binuclear complex {[Gd（H2O）6]2[Q6（H2O）]}C16·4H2O, where Q6 represents cucurbit[6]uril, has been synthesized and characterized by X-ray diffraction. The crystal structure shows that the complex has an extended cucurbit[6]uril-bridged structure consisting of two gadolinium（Ⅲ） ions, in which each gadolinium（Ⅲ） ion is coordinated with two neighboring carbonylic oxygen atoms of Q6 and six oxygen atoms of water molecules that leans toward one side of the portal. One disordered vip water molecule resides in the Q6 molecule cavity and occupies two different positions. Hydrogen bonds assemble the complcx to threedimensional supramolecular structure.展开更多
A new terbium(Ⅲ complex Tb(C20H14O3N)3(C12H8N2)（H2O）·H2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclin...A new terbium(Ⅲ complex Tb(C20H14O3N)3(C12H8N2)（H2O）·H2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034（6）, b = 16.2465（8）, c = 16.4427（8） ?, α = 73.168（5）o, β = 88.655（4）o, γ = 82.865（4）o, V = 2943.7（3） ?3, Dc = 1.494 g/cm3, Z = 2, μ（MoK α） = 1.272 mm-1, F（000） = 1348, the final R = 0.0535 and w R = 0.0809. The Tb（Ⅲ） ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb3+: 5D4 → 7F6（491 nm）, 5D4 → 7F5（546 nm）, 5D4 → 7F4（585 nm） and 5D4→7F3（621 nm）. Also reported are the magnetic and thermal stability properties of the complex.展开更多
As DNA cleavage agent, a new diiron（Ⅲ） complex （Fe2Lb）, in which a DNA-intercalator （pyrene） is covalently linked to a diferric moiety, has been synthesized and characterized. The DNA-binding property and DNA c...As DNA cleavage agent, a new diiron（Ⅲ） complex （Fe2Lb）, in which a DNA-intercalator （pyrene） is covalently linked to a diferric moiety, has been synthesized and characterized. The DNA-binding property and DNA cleavage activity of the complex have also been investigated.展开更多
Two new mononuclear lanthanide（Ⅲ） complexes Ln（pytz）3（H2O）3·（H2O）3.5[Ln=Tb（1）;Eu（2）;Hpytz=5-（2-pyridyl）tetrazole] were synthesized by reacting Hpytz with the corresponding lanthanide（Ⅲ） ions and...Two new mononuclear lanthanide（Ⅲ） complexes Ln（pytz）3（H2O）3·（H2O）3.5[Ln=Tb（1）;Eu（2）;Hpytz=5-（2-pyridyl）tetrazole] were synthesized by reacting Hpytz with the corresponding lanthanide（Ⅲ） ions and characterized.The single crystal X-ray diffraction analysis reveals that complexes 1 and 2 are isostructural and the lanthanide（Ⅲ） ions in both complexes 1 and 2 are nine-coordinated,with three oxygen atoms of three coordination water molecules and six nitrogen atoms of three pytz ligands,forming a monocapped square antiprism.Extensive hydrogen bonds exist,resulting in a three-dimensional supramolecular network structure by hydrogen-bonds in both complexes 1 and 2,respectively.Complex 1 exhibits typical green fluorescence of Tb（Ⅲ） ion and complex 2 red fluorescence of Eu（Ⅲ） ion,in solid state at room temperature.展开更多
A new unsymmetrical Schiff base ligand (H2LLi) was synthesized using L-lysine, salicylaldehyde and 2-hydroxy-1-naphthaldehyde. Three solid metal complexes of this ligand \[Ln(H2L)(NO3)\] NO3·2H2O (Ln=La, Sm, Ho) ...A new unsymmetrical Schiff base ligand (H2LLi) was synthesized using L-lysine, salicylaldehyde and 2-hydroxy-1-naphthaldehyde. Three solid metal complexes of this ligand \[Ln(H2L)(NO3)\] NO3·2H2O (Ln=La, Sm, Ho) have been prepared and characterized by elemental analyses, IR spectra, UV spectra, TG-DTG and molar conductance. The antibacterial activities of the ligand and its complexes are also studied. The antibacterial experiments indicate that the ligand and its complexes possess antibacterial activity against Escherichia coli, Staphylococcus aureus and Bacillus subtilis and that the complexes have higher activity than those of the ligand.展开更多
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
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.
基金the support of Natural Science Foundation of China(No.22276123)the Shanghai Engineering Research Center of Water Environment Simulation and Ecological Restoration(No.WESER-202201)the Postdoctoral Fellowship Program of CPSF(No.GZB20240456)。
文摘Carbon dot(CD)is an edge-bound,nanometer-sized carbon material possessing unique optical and electronic properties,making it promising metal-free,environmentally benign.In this study,we identified a highly hydrophilic CD complexed with Fe(Ⅲ)via carboxyl groups to form CD-COOFeⅢ,which exhibited remarkably enhanced Fenton-like reaction performance boosted by visible light irradiation.CD-COOFeⅢenabled high activity in the visible region beyondλ>420 nm,and maintained stable oxidation efficiency in the presence of H_(2)O_(2)over at least ten cycles.The capacity of electrons transferred from photo-excited CD to reduce Fe(Ⅲ)was calculated to be 1.1 mmol/g of CD.Furthermore,the quantum yield(QY)of solarto-Fe(Ⅱ)conversion reached an impressive 87.7%.These findings not only suggest a viable strategy for efficient conversion of solar-to-chemical using a CD-COOFeⅢcomplex in visible light boosted Fenton-like oxidation reaction,but also provide insight for understanding the effect of nanosized artificial and/or natural carbon materials in iron recycling in a natural surface environment.
基金Supported by the Natural Science Foundation of Hebei Province(No.2 0 2 140 ) and Hebei Education Departm ent(No.2 0 0 112 1)
文摘The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).
基金supported by the Construct Program of the Key Discipline in Hunan Province
文摘A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.
基金Project supported by Vietnam Academy of Science and Technology(VAST03.03/18-19)
文摘The luminescent rare earth(RE)complex based multifunctional nanocomposites offer new potential applications of multimodal imaging(magnetic resonance imaging(MRI),fluorescent bioimaging,etc.)that can be associated with therapeutic activities.In this study,we report some results obtained with novel multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites that are composed of europium(Ⅲ)complex with 1-(2-naphthoyl)-3,3,3-trifluoroacetone ligands(NTA)(Eu(NTA)3)and superparamagnetic Fe3O4 nanoparticles.These nanocomposites were functionalized with an amine group for biomedicine application.The multifunctional Fe3O4/Si-amine/Eu(NTA)3 nanocomposites exhibit both good magnetic behavior of Fe3O4 nanoparticles as a core and strong fluorescent property of europium(Ⅲ)complex.Their characterizations were analyzed by XRD,SEM,EDX and FTIR spectra.The optical properties were studied in detail by UV-VIS spectra and luminescent emission spectra.The magnetic property was estimated by VMS.The effect of concentrations of luminescent Eu(NTA)3 complex on luminescent and magnetic properties is discussed.
基金Ph.D. Programme at the Department of Chemistry, University of Kerala, India
文摘A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].
基金supported by the cooperative project of Hengyang Normal University with Hengyang Yile New Materials Co.,Ltd.(No.HXKJ201905)
文摘A new europium(Ⅲ)complex Eu_(2)(C_(15)H_(11)O_(3))_(6)(C_(12)H_(8)N_(2))_(2)has been synthesized with 2-(4-Methylbenzoyl)benzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2_(1/n),a=15.1238(5),b=13.5928(4),c=22.9840(7)A,β=104.132(3)o,V=4582.0(2)A3,Dc=1.522 g/cm^(3),Z=4,μ(Mo Kα)=1.433 mm^(-1),F(000)=2128,the final R=0.0447 and wR=0.0826.The Eu(Ⅲ)ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu^(3+):5 D0→7 F1(594 nm)and 5 D0→7 F2(617 nm).The complex is an antiferromagnetism system in the range of 150~300 K.Also reported in the paper is the thermal stability property of the title complex.
基金financially supported by the National Key R&D Program of China (No. 2021YFA1501700)the National Natural Science Foundation of China+1 种基金Basic Science Center Program (No.51988102)the National Natural Science Foundation of China (No. 52073272)
文摘Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.
文摘Two complexes[Ni(L)(OAc)](1)and[Co(L)2]Cl·4CH3OH(2)(HL=2-aceto-3-methylpyrazine N-(4-fluorophenyl)thiosemicarbazone)have been synthesized and structurally determined by single-crystal X-ray diffraction,elemental analysis and IR spectroscopy.X-ray diffraction analysis results show that the Ni(Ⅱ)ion in complex 1 with a distorted square planar geometry is surrounded by one anionic TSC ligand with NNS donor set and one monodentate acetate.By contrast,Co(Ⅲ)ion coordinates with two tridentate TSC ligands,and thus possessing a distorted octahedron coordination geometry.Moreover,the fluorescence spectra indicate that the interactions of complexes 1 and 2 with DNA are stronger than that of the ligand HL.CCDC:1848437,1;1848438,2.
基金Project supported by the National Natural Science Foundation of China (90406021, 50903028)Science and Technology Bureau of Heilongjiang Province (QC08C10)
文摘The bidentate phosphine oxide ligand 1,8-bis(diphenylphosphino) naphthalene oxide (NAPO) and its EuⅢ complex 1 Eu(TTA)3(NAPO) (TTA=2-thenoyltrifluoroacetonate) were chosen to study the effect of bidentate phosphine oxide ligand on the photophysical properties of the corresponding complex. The intramolecular energy transfer processes of 1 were studied. The investigation showed that with bidentate structure NAPO could suppress solvent-induced quenching by enforcing the ligand-ligand interaction and the rigidi...
文摘Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.
基金supported by the National Natural Science Foundation of China(No.21671114 and U1804131)Natural Science Foundation of Henan Province(No.182300410166,182102310909 and 182102310897)
文摘A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090（2）, b = 8.0824（13）, c = 15.5591（17） ?, V = 1775.4（5） ?3, Mr = 576.22, Dc = 2.156 g/cm3, μ（Mo Kα） = 4.059 mm-1, F（000） = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections（I > 2σ（I））. Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium（Ⅲ） ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.
文摘A new aryl amide type tetrapodal ligand L (1, 1, 1, 1 tetrakis-{[(2 benzylaminoformyl) phenoxyl]methyl}methane) and its europium and terbium nitrate complexes were synthesized. The luminescence properties of these complexes were also studied.
文摘A complex of terbium(Ⅲ) with Schiff base salicylaldehyde-taurine and 1,10-phenanthroline was synthesized. The molecular formula was [Tb (sal-taurine) (1,10-phen) (NO_3)]·2H_2O (sal=salicylaldehyde, 1,10-phen=1,10-phenanthroline). The composition of the title complex was determined by elemental analysis and EDTA volumetic analysis. IR, Molar conductivity and X-ray powder diffraction were performed for its characterizations. The thermal decomposition kinetics of the complex were investigated under non-isothermal condition using the Achar differential method and the Coats-Redfern integral method. The kinetic equation for the second step corresponds to the mechanisms of the Zhuralev, Lesokin and Templman equation were obtained.
基金supported by the National Natural Science Foundation of China(No.20471056)
文摘A new cucurbit[6]uril bridsed binuclear complex {[Gd（H2O）6]2[Q6（H2O）]}C16·4H2O, where Q6 represents cucurbit[6]uril, has been synthesized and characterized by X-ray diffraction. The crystal structure shows that the complex has an extended cucurbit[6]uril-bridged structure consisting of two gadolinium（Ⅲ） ions, in which each gadolinium（Ⅲ） ion is coordinated with two neighboring carbonylic oxygen atoms of Q6 and six oxygen atoms of water molecules that leans toward one side of the portal. One disordered vip water molecule resides in the Q6 molecule cavity and occupies two different positions. Hydrogen bonds assemble the complcx to threedimensional supramolecular structure.
基金supported by the cooperative project of Hengyang Normal University with Hengyang Yile New Materials Co.,Ltd.(HXKJ201905)the Natural Science Foundation of Hunan Province(2019JJ60021,2019JJ50013)+1 种基金the Scientific Research Found of Hunan Provincial Education Department of China(17A049)the Industry and Research Key Project of Hengyang City(2018k KJ016,2017KJ155,2017KJ193)
文摘A new terbium(Ⅲ complex Tb(C20H14O3N)3(C12H8N2)（H2O）·H2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034（6）, b = 16.2465（8）, c = 16.4427（8） ?, α = 73.168（5）o, β = 88.655（4）o, γ = 82.865（4）o, V = 2943.7（3） ?3, Dc = 1.494 g/cm3, Z = 2, μ（MoK α） = 1.272 mm-1, F（000） = 1348, the final R = 0.0535 and w R = 0.0809. The Tb（Ⅲ） ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb3+: 5D4 → 7F6（491 nm）, 5D4 → 7F5（546 nm）, 5D4 → 7F4（585 nm） and 5D4→7F3（621 nm）. Also reported are the magnetic and thermal stability properties of the complex.
文摘As DNA cleavage agent, a new diiron（Ⅲ） complex （Fe2Lb）, in which a DNA-intercalator （pyrene） is covalently linked to a diferric moiety, has been synthesized and characterized. The DNA-binding property and DNA cleavage activity of the complex have also been investigated.
基金Supported by the National Natural Science Foundation of China(No.20975009)
文摘Two new mononuclear lanthanide（Ⅲ） complexes Ln（pytz）3（H2O）3·（H2O）3.5[Ln=Tb（1）;Eu（2）;Hpytz=5-（2-pyridyl）tetrazole] were synthesized by reacting Hpytz with the corresponding lanthanide（Ⅲ） ions and characterized.The single crystal X-ray diffraction analysis reveals that complexes 1 and 2 are isostructural and the lanthanide（Ⅲ） ions in both complexes 1 and 2 are nine-coordinated,with three oxygen atoms of three coordination water molecules and six nitrogen atoms of three pytz ligands,forming a monocapped square antiprism.Extensive hydrogen bonds exist,resulting in a three-dimensional supramolecular network structure by hydrogen-bonds in both complexes 1 and 2,respectively.Complex 1 exhibits typical green fluorescence of Tb（Ⅲ） ion and complex 2 red fluorescence of Eu（Ⅲ） ion,in solid state at room temperature.
文摘A new unsymmetrical Schiff base ligand (H2LLi) was synthesized using L-lysine, salicylaldehyde and 2-hydroxy-1-naphthaldehyde. Three solid metal complexes of this ligand \[Ln(H2L)(NO3)\] NO3·2H2O (Ln=La, Sm, Ho) have been prepared and characterized by elemental analyses, IR spectra, UV spectra, TG-DTG and molar conductance. The antibacterial activities of the ligand and its complexes are also studied. The antibacterial experiments indicate that the ligand and its complexes possess antibacterial activity against Escherichia coli, Staphylococcus aureus and Bacillus subtilis and that the complexes have higher activity than those of the ligand.
