A new cyclometalated iridium(III) complex with the formula [Ir(DPQ)2(acac)] (DPQ= 2,3-diphenylquinoxaline; acac=acetylacetone) was prepared. The structure of the complex was confirmed by Elemental Analysis (EA), 1H NM...A new cyclometalated iridium(III) complex with the formula [Ir(DPQ)2(acac)] (DPQ= 2,3-diphenylquinoxaline; acac=acetylacetone) was prepared. The structure of the complex was confirmed by Elemental Analysis (EA), 1H NMR, and mass spectroscopy (MS). The UV-vis absorption and photoluminescent properties of the complex were investigated.展开更多
Based on cryogenic FT-IR spectroscopic studies of hydrogen bonds in cholic acid, two-dimensional FT-IR spectroscopy was applied to enhance our understanding of the hydrogen bonds of cholic acid. Fine spectral structu...Based on cryogenic FT-IR spectroscopic studies of hydrogen bonds in cholic acid, two-dimensional FT-IR spectroscopy was applied to enhance our understanding of the hydrogen bonds of cholic acid. Fine spectral structures were revealed by asynchronous 2D FT-IR spectra. The co-relationship among various bands was discussed according to the synchronous 2D FT-IR spectrum.展开更多
A 3d 4f complex [La(DMF) 6(H 2O) 3]·2H 2O (DMF=N,N dimethylformamide) was prepared and characterized by single crystal structure analysis. Single crystal X ray diffraction analysis reveals that the presen...A 3d 4f complex [La(DMF) 6(H 2O) 3]·2H 2O (DMF=N,N dimethylformamide) was prepared and characterized by single crystal structure analysis. Single crystal X ray diffraction analysis reveals that the present complex contains 3- and [La(DMF) 6(H 2O) 3] 3+ ionic pairs. The La(Ⅲ) ion is nine coordinate, and is coordinated by seven oxygen atoms of three water molecules and six DMF molecules. Each terminal CN ligand of the 3- entity is hydrogen bonded to oxygen atoms of the coordinated and lattice water molecules producing a three dimensional network. Crystal data for [La(DMF) 5(H 2O) 3]·2H 2O (C 24 H 52 CrLaN 12 O 11 =875.69): orthorhombic, space group Cmca, with lattice parameters of a =1.9346(2) nm, b =2.8902(2) nm, c =1.4825(2) nm, V =8.289(2) nm 3, Z =8, S =1.074, ρ calc =1.403 g·cm -3 , R 1=0.046, wR 2=0 117 based on 244 parameters for 5083 observed ( I >2 σ ( I )) reflections.展开更多
Two one dimensional heterometallic coordination polymers {[CuEr(Gly) 5(H 2O) 2](ClO 4) 5·H 2O} n (1) and {[Cu 2Gd 2(Gly) 10 (H 2O) 4](ClO 4) 10 ·4H 2O} n (2) (Gly = glycine) we...Two one dimensional heterometallic coordination polymers {[CuEr(Gly) 5(H 2O) 2](ClO 4) 5·H 2O} n (1) and {[Cu 2Gd 2(Gly) 10 (H 2O) 4](ClO 4) 10 ·4H 2O} n (2) (Gly = glycine) were synthesized and structurally and characterized magnetically. Complex 1 crystallizes in a triclinic space group of P 1 with a =1.1769(2) nm, b =1 2289(3) nm, c = 1.4452(3) nm, α = 89.90(3)°, β = 71.88(3)°, γ = 62.15(3)°, and Z =2. The carboxyl groups of glycine molecules take two coordination modes. The first one acts as a bidentate bridging ligand only. The second is a tridentate bridge that coordinates to three different metal ions. Each erbium ion is eight coordinated, taking a distorted square antiprism arrangement. The copper ion has a square pyramidal coordination polyhedron. The topological structure of complex 2 is similar to complex 1, but there are some disparities in the bond lengths and bond angles. It is also triclinic space group of P 1 with a = 1.2479(3) nm, b = 1.4489(3) nm, c =2.0885(4) nm, α = 109.56(3)°, β = 93.75(3)°, γ = 93.54(3)°, and Z =2. Variable temperature susceptibility measurements show that there is a weak ferromagnetic interaction between the Gd 3+ and Cu 2+ ions in complex 2.展开更多
Two cyano bridged dimeric 4f 3d complexes [Nd(DMF) 4(H 2O) 3Co(CN) 6]·H 2O (A) and [Sm(pyr) 4(H 2O) 3Cr(CN) 6]·2H 2O (B) (DMF=N,N dimethylformamide, pyr=2 pyrrolidone) were prepared and structu...Two cyano bridged dimeric 4f 3d complexes [Nd(DMF) 4(H 2O) 3Co(CN) 6]·H 2O (A) and [Sm(pyr) 4(H 2O) 3Cr(CN) 6]·2H 2O (B) (DMF=N,N dimethylformamide, pyr=2 pyrrolidone) were prepared and structurally characterized. Single crystal X ray diffraction analysis revealed that the complexes contain cyano bridged 3 and [Ln(L) 4(H 2O) 3] 3+ groups. The Ln 3+ is eight coordinate, and is coordinated by seven oxygen atoms of three water molecules and four organic ligands (DMF or pyr). Each terminal CN ligand of the 3- entity is hydrogen bonded to some oxygen atoms of the coordinated water molecules yielding a hydrogen bonded three dimensional network. Crystal data for A: monoclinic, space group P 2(1)/ n , a = 1.7525(4) nm, b =0.8879(2) nm, c =1.9876(4) nm, β =95.92(3)°, V =3.0763(12) nm 3, Z =4, D c= 1.563 mg·m -3 . Complex B crystallizes in the P 1 space group, with lattice parameters of a =1.22720(4) nm, b =1.45550(8) nm, c =0.91310(4) nm, α =92.5869(17)°, β = 90.9569(12)°, γ =89.822(3)°, V =1.62908(13) nm 3, Z =2, D c=1.608 mg·m -3 .展开更多
Binary and ternary terbium complexes were synthesized: Tb(N PA) 3·4H 2O and Tb(N PA) 3(phen·2H 2O (N HPA = N phenyl 2 aminobenzoic acid and phen = 1,10 phenanthroline). These complexes were introd...Binary and ternary terbium complexes were synthesized: Tb(N PA) 3·4H 2O and Tb(N PA) 3(phen·2H 2O (N HPA = N phenyl 2 aminobenzoic acid and phen = 1,10 phenanthroline). These complexes were introduced into inorganic polymeric porous silica matrix by the sol gel method. The luminescence behavior of the complexes in silica gels was compared with the corresponding solid state complexes by means of emission, excitation spectra and luminescence lifetimes. The result indicates that the terbium ions show fewer emission lines and lower emission intensities in the silica gel than those in pure terbium complexes. The lifetimes of terbium ions in silica gel doped with terbium complexes become longer than those of terbium complexes.展开更多
The cyclic voltammetry and potentiostatic electrolysis were used toinvestigate the preparing of Dy-Bi alloy films in LiCl-DMSO (dimethylsulfoxide) system. The effectsof several factors including the potential of depos...The cyclic voltammetry and potentiostatic electrolysis were used toinvestigate the preparing of Dy-Bi alloy films in LiCl-DMSO (dimethylsulfoxide) system. The effectsof several factors including the potential of deposition, concentrations of main salts, and theconcentration ratio of DyCl_3 to Bi(NO_3)_3 were studied. Dy-Bi alloy films containing 4.82%-80.62%(mass fraction) dysprosium were prepared in DyCl_3-Bi(NO_3)_3-LiCl-DMSO system by controlling thesystem composition and deposition conditions. The films are gray, uniform, metallic luster andadhere firmly to the copper substrates analyzed by SEM (scanning electron microscope), EDS (X-rayenergy dispersive analysis), and XRD (X-ray diffraction). After heat treatment at 718 K for 1 h, thealloy phase of Dy-Bi was found in XRD patterns.展开更多
A new photoresponsive D--A dye, mPS, has been designed and synthesized. Compared to the parent dye PS, IPCE values in the region from 400 nm to 560 nm was greatly improved upon changing the attaching group from the p...A new photoresponsive D--A dye, mPS, has been designed and synthesized. Compared to the parent dye PS, IPCE values in the region from 400 nm to 560 nm was greatly improved upon changing the attaching group from the p- position to the o- position of the p-conjugation bridge. A solar cell based on mPS generated a remarkably high overall yield of 5.4% under irradiation of 80.0 mW cm-2 white light from a Xe lamp. Compared with PS, the overall yield ?increased by 64%.展开更多
A kind of azo-containing resin(Azo-R)was synthesized by a simple way through the coupling reaction of 2-nitro-N-methyldiphenylamine-4-diazoresin(NDR)with phenol,and a new covalentely attached multilayer film from Azo-...A kind of azo-containing resin(Azo-R)was synthesized by a simple way through the coupling reaction of 2-nitro-N-methyldiphenylamine-4-diazoresin(NDR)with phenol,and a new covalentely attached multilayer film from Azo-R asH-donor and photosensitive diazoresin,diphenylamine-4-diazoresin(DR)as H-acceptor via H-bonding attraction by self-assembly technique has been fabricated.Following the decomposition of diazonium group of DR under exposure to UVlight,the H-bonds between the layers of the film convert to covalent bonds and the film becomes very stable toward polarsolvents or electrolyte aqueous solutions.Thus the UV-irradiated azo-containing films can be used to measure photocurrentin a conventional three-electrode photoelectrochemical cell using KCl as supporting electrolyte.It was confirmed that theazo-containing multilayer film is responsible for the photocurrent generation.展开更多
The bilayer organic light-emitting diode(OLED) with a blue fluorescent lanthanum complex, tris(1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone)-(2,2′-dipyridyl) lanthanum [La(PMIP) 3(Bipy)], as a light emitting material...The bilayer organic light-emitting diode(OLED) with a blue fluorescent lanthanum complex, tris(1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone)-(2,2′-dipyridyl) lanthanum [La(PMIP) 3(Bipy)], as a light emitting material and N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine(TPD) as a hole transporting material emits bright green light instead of blue light. The data of the absorption, the photoluminescence(PL) and the photoluminescence excitation(PLE) spectra of TPD, La(PMIP) 3(Bipy) and the mixture of TPD and La(PMIP) 3(Bipy)(molar ratio 1∶1) prove that the electroluminescent emission originates from the exciplex on the interface between TPD and La(PMIP) 3(Bipy). By improving device configuration with tris(8-hydroxyquinoline) aluminum(ALQ) as an electron transporting material, a maximum luminance of 800 cd/m 2 was obtained.展开更多
The atomic structure of a novel rare earth complex consisting of Nd and the sulfur-containing ligand pipdtc (C5H10NCS2^-) has been studied with extended x-ray absortpiton fine structure(EXAFS) and x-ray diffraction te...The atomic structure of a novel rare earth complex consisting of Nd and the sulfur-containing ligand pipdtc (C5H10NCS2^-) has been studied with extended x-ray absortpiton fine structure(EXAFS) and x-ray diffraction techniques.The complex of formula Nd(pipdtc)4N(CH3)4 crystallizaes in the monoclinic space group P21/n with the following lattice parameters,a=22.685(2),b=20.332(2),c=17.1270(10)A,β=100.570(10)°.Z=8,the calculated density is 1.47g/cm^3,A new derivative method is used to remove the piost-edge absorption background including the multielectron excitation effect.The EXAFS results demonstrate that there are about eight S and four O atoms around Nd with the Nd-S bond length of 2.916A and the Nd-O bond length of 2.415A,respectively.This implies that the powder of this complex is not stable and is easy to oxidize in air.The possible change of structure before and after oxidation is discussed.展开更多
The microstructures of loaded organic phases of three quaternary amine solvent extraction systems for gold,which were N263-xylene,N263-tributyl phosphate(TBP)-dodecane and N263-2 -ethylhexanol (isooctanol)-dodecane(N2...The microstructures of loaded organic phases of three quaternary amine solvent extraction systems for gold,which were N263-xylene,N263-tributyl phosphate(TBP)-dodecane and N263-2 -ethylhexanol (isooctanol)-dodecane(N263-trialkylmethylammonium chloride;alkyl=C8-C10),were studied by Fourier transform infrared (FTIR) spectroscopy and extended X-ray abso\rption fine structure(EXAFS) spectroscopy. According to the EXAFS results,it was found that the gold coordination environment was the same before and after extraction.However,the C≡N stretching vibrations of Au(CN)2-were also found to be different,In order to explain the differences in the IR characteristics of C≡N in the three extraction systems,three microstructure models are proposed.For the N263-xylene system,the model is a simple ion pair.For the other two systems with a modifier(TBP and isooctanol),the models are two supramolecular structues based on hydrogen bonding between the modifier and Au(CN)2^-.Some related work such as on the hydration of acetonitrile and the fine structure of C≡N in solid K Au(CN)2 was also performed in order to offer additional supporting evidence for the reliability of the proposed models.展开更多
文摘A new cyclometalated iridium(III) complex with the formula [Ir(DPQ)2(acac)] (DPQ= 2,3-diphenylquinoxaline; acac=acetylacetone) was prepared. The structure of the complex was confirmed by Elemental Analysis (EA), 1H NMR, and mass spectroscopy (MS). The UV-vis absorption and photoluminescent properties of the complex were investigated.
基金The Project was supported by State Key Project of Basic Research MOST G1998061307 the National Natural Science Foundation of China (NSFC+8 种基金 grant No. 59733060 59873030 59953001 59903008 29671002 39730160 20023005 29901002) and Major Proj
文摘Based on cryogenic FT-IR spectroscopic studies of hydrogen bonds in cholic acid, two-dimensional FT-IR spectroscopy was applied to enhance our understanding of the hydrogen bonds of cholic acid. Fine spectral structures were revealed by asynchronous 2D FT-IR spectra. The co-relationship among various bands was discussed according to the synchronous 2D FT-IR spectrum.
文摘A 3d 4f complex [La(DMF) 6(H 2O) 3]·2H 2O (DMF=N,N dimethylformamide) was prepared and characterized by single crystal structure analysis. Single crystal X ray diffraction analysis reveals that the present complex contains 3- and [La(DMF) 6(H 2O) 3] 3+ ionic pairs. The La(Ⅲ) ion is nine coordinate, and is coordinated by seven oxygen atoms of three water molecules and six DMF molecules. Each terminal CN ligand of the 3- entity is hydrogen bonded to oxygen atoms of the coordinated and lattice water molecules producing a three dimensional network. Crystal data for [La(DMF) 5(H 2O) 3]·2H 2O (C 24 H 52 CrLaN 12 O 11 =875.69): orthorhombic, space group Cmca, with lattice parameters of a =1.9346(2) nm, b =2.8902(2) nm, c =1.4825(2) nm, V =8.289(2) nm 3, Z =8, S =1.074, ρ calc =1.403 g·cm -3 , R 1=0.046, wR 2=0 117 based on 244 parameters for 5083 observed ( I >2 σ ( I )) reflections.
文摘Two one dimensional heterometallic coordination polymers {[CuEr(Gly) 5(H 2O) 2](ClO 4) 5·H 2O} n (1) and {[Cu 2Gd 2(Gly) 10 (H 2O) 4](ClO 4) 10 ·4H 2O} n (2) (Gly = glycine) were synthesized and structurally and characterized magnetically. Complex 1 crystallizes in a triclinic space group of P 1 with a =1.1769(2) nm, b =1 2289(3) nm, c = 1.4452(3) nm, α = 89.90(3)°, β = 71.88(3)°, γ = 62.15(3)°, and Z =2. The carboxyl groups of glycine molecules take two coordination modes. The first one acts as a bidentate bridging ligand only. The second is a tridentate bridge that coordinates to three different metal ions. Each erbium ion is eight coordinated, taking a distorted square antiprism arrangement. The copper ion has a square pyramidal coordination polyhedron. The topological structure of complex 2 is similar to complex 1, but there are some disparities in the bond lengths and bond angles. It is also triclinic space group of P 1 with a = 1.2479(3) nm, b = 1.4489(3) nm, c =2.0885(4) nm, α = 109.56(3)°, β = 93.75(3)°, γ = 93.54(3)°, and Z =2. Variable temperature susceptibility measurements show that there is a weak ferromagnetic interaction between the Gd 3+ and Cu 2+ ions in complex 2.
文摘Two cyano bridged dimeric 4f 3d complexes [Nd(DMF) 4(H 2O) 3Co(CN) 6]·H 2O (A) and [Sm(pyr) 4(H 2O) 3Cr(CN) 6]·2H 2O (B) (DMF=N,N dimethylformamide, pyr=2 pyrrolidone) were prepared and structurally characterized. Single crystal X ray diffraction analysis revealed that the complexes contain cyano bridged 3 and [Ln(L) 4(H 2O) 3] 3+ groups. The Ln 3+ is eight coordinate, and is coordinated by seven oxygen atoms of three water molecules and four organic ligands (DMF or pyr). Each terminal CN ligand of the 3- entity is hydrogen bonded to some oxygen atoms of the coordinated water molecules yielding a hydrogen bonded three dimensional network. Crystal data for A: monoclinic, space group P 2(1)/ n , a = 1.7525(4) nm, b =0.8879(2) nm, c =1.9876(4) nm, β =95.92(3)°, V =3.0763(12) nm 3, Z =4, D c= 1.563 mg·m -3 . Complex B crystallizes in the P 1 space group, with lattice parameters of a =1.22720(4) nm, b =1.45550(8) nm, c =0.91310(4) nm, α =92.5869(17)°, β = 90.9569(12)°, γ =89.822(3)°, V =1.62908(13) nm 3, Z =2, D c=1.608 mg·m -3 .
文摘Binary and ternary terbium complexes were synthesized: Tb(N PA) 3·4H 2O and Tb(N PA) 3(phen·2H 2O (N HPA = N phenyl 2 aminobenzoic acid and phen = 1,10 phenanthroline). These complexes were introduced into inorganic polymeric porous silica matrix by the sol gel method. The luminescence behavior of the complexes in silica gels was compared with the corresponding solid state complexes by means of emission, excitation spectra and luminescence lifetimes. The result indicates that the terbium ions show fewer emission lines and lower emission intensities in the silica gel than those in pure terbium complexes. The lifetimes of terbium ions in silica gel doped with terbium complexes become longer than those of terbium complexes.
基金This project was financially supported by the Natural Science Foundation of Guangdong Province (No. 01125) and State Key Lab of Rare Earths Material Chemistry and Applications, Beijing 100871, China.
文摘The cyclic voltammetry and potentiostatic electrolysis were used toinvestigate the preparing of Dy-Bi alloy films in LiCl-DMSO (dimethylsulfoxide) system. The effectsof several factors including the potential of deposition, concentrations of main salts, and theconcentration ratio of DyCl_3 to Bi(NO_3)_3 were studied. Dy-Bi alloy films containing 4.82%-80.62%(mass fraction) dysprosium were prepared in DyCl_3-Bi(NO_3)_3-LiCl-DMSO system by controlling thesystem composition and deposition conditions. The films are gray, uniform, metallic luster andadhere firmly to the copper substrates analyzed by SEM (scanning electron microscope), EDS (X-rayenergy dispersive analysis), and XRD (X-ray diffraction). After heat treatment at 718 K for 1 h, thealloy phase of Dy-Bi was found in XRD patterns.
基金supported by the State Key Program of Fundamental Research(G1998061308,and 2002AA3024030).
文摘A new photoresponsive D--A dye, mPS, has been designed and synthesized. Compared to the parent dye PS, IPCE values in the region from 400 nm to 560 nm was greatly improved upon changing the attaching group from the p- position to the o- position of the p-conjugation bridge. A solar cell based on mPS generated a remarkably high overall yield of 5.4% under irradiation of 80.0 mW cm-2 white light from a Xe lamp. Compared with PS, the overall yield ?increased by 64%.
基金This work is financially supported by NSFC(No.2027400250173002).
文摘A kind of azo-containing resin(Azo-R)was synthesized by a simple way through the coupling reaction of 2-nitro-N-methyldiphenylamine-4-diazoresin(NDR)with phenol,and a new covalentely attached multilayer film from Azo-R asH-donor and photosensitive diazoresin,diphenylamine-4-diazoresin(DR)as H-acceptor via H-bonding attraction by self-assembly technique has been fabricated.Following the decomposition of diazonium group of DR under exposure to UVlight,the H-bonds between the layers of the film convert to covalent bonds and the film becomes very stable toward polarsolvents or electrolyte aqueous solutions.Thus the UV-irradiated azo-containing films can be used to measure photocurrentin a conventional three-electrode photoelectrochemical cell using KCl as supporting electrolyte.It was confirmed that theazo-containing multilayer film is responsible for the photocurrent generation.
基金the National Natural Science Foundation of China(Nos.2 0 2 2 110 1,2 0 4 710 0 4 ,5 0 372 0 0 2 ) ,State"86 3"Program(No.2 0 2 2 AA32 4 0 80 ) and the Doctorial Program Foundation of High Education(No.2 0 0 30 0 0 10 6 5 )
文摘The bilayer organic light-emitting diode(OLED) with a blue fluorescent lanthanum complex, tris(1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone)-(2,2′-dipyridyl) lanthanum [La(PMIP) 3(Bipy)], as a light emitting material and N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine(TPD) as a hole transporting material emits bright green light instead of blue light. The data of the absorption, the photoluminescence(PL) and the photoluminescence excitation(PLE) spectra of TPD, La(PMIP) 3(Bipy) and the mixture of TPD and La(PMIP) 3(Bipy)(molar ratio 1∶1) prove that the electroluminescent emission originates from the exciplex on the interface between TPD and La(PMIP) 3(Bipy). By improving device configuration with tris(8-hydroxyquinoline) aluminum(ALQ) as an electron transporting material, a maximum luminance of 800 cd/m 2 was obtained.
文摘The atomic structure of a novel rare earth complex consisting of Nd and the sulfur-containing ligand pipdtc (C5H10NCS2^-) has been studied with extended x-ray absortpiton fine structure(EXAFS) and x-ray diffraction techniques.The complex of formula Nd(pipdtc)4N(CH3)4 crystallizaes in the monoclinic space group P21/n with the following lattice parameters,a=22.685(2),b=20.332(2),c=17.1270(10)A,β=100.570(10)°.Z=8,the calculated density is 1.47g/cm^3,A new derivative method is used to remove the piost-edge absorption background including the multielectron excitation effect.The EXAFS results demonstrate that there are about eight S and four O atoms around Nd with the Nd-S bond length of 2.916A and the Nd-O bond length of 2.415A,respectively.This implies that the powder of this complex is not stable and is easy to oxidize in air.The possible change of structure before and after oxidation is discussed.
文摘The microstructures of loaded organic phases of three quaternary amine solvent extraction systems for gold,which were N263-xylene,N263-tributyl phosphate(TBP)-dodecane and N263-2 -ethylhexanol (isooctanol)-dodecane(N263-trialkylmethylammonium chloride;alkyl=C8-C10),were studied by Fourier transform infrared (FTIR) spectroscopy and extended X-ray abso\rption fine structure(EXAFS) spectroscopy. According to the EXAFS results,it was found that the gold coordination environment was the same before and after extraction.However,the C≡N stretching vibrations of Au(CN)2-were also found to be different,In order to explain the differences in the IR characteristics of C≡N in the three extraction systems,three microstructure models are proposed.For the N263-xylene system,the model is a simple ion pair.For the other two systems with a modifier(TBP and isooctanol),the models are two supramolecular structues based on hydrogen bonding between the modifier and Au(CN)2^-.Some related work such as on the hydration of acetonitrile and the fine structure of C≡N in solid K Au(CN)2 was also performed in order to offer additional supporting evidence for the reliability of the proposed models.
