Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem ...Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem crossing(ISC) and suppressing non-radiative transitions. In supramolecular chemistry, the control and regulation of molecular recognition based on the role of the host and guest in supramolecular polymers matrix, has attracted much attention. Recently, researchers have successfully achieved room temperature phosphorescence of pure organic complexes through host-guest interactions. The host molecule specifically includes the phosphorescent guest to reduce non-radiative transitions and enhance room temperature phosphorescence emission. This review aims to describe the developments and achievements of pure organic room temperature phosphorescence systems through the mechanism of host-guest interactions in recent years, and demonstrates the exploration and pursuit of phosphorescent materials of researchers in different fields.展开更多
Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-r...Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-ray single-crystal diffraction analysis. Complex 1 belongs to the trigonal system, space group R-3 with a = b = 19.2730（5）, c = 23.6890（13）A^°, V= 7620.4（5） A^°^3, Z = 6, Dc= 1.553 g/cm^3,μ= 1.518 mm^-1, F（000） = 3600, R = 0.0238 and wR = 0.0636. Complex 2 is of monoelinie system, space group P21/c with a = 13.7550（8）, b = 11.5425（7）, c = 12.7876（7）A^°, β= 93.585（1）°, V = 2026.3（2） A^°^3, Z = 4, Dc= 1.548 g/cm^3,μ = 1.286 mm^-1, F（000） = 976, R = 0.0298 and wR = 0.0722. Complex 1 is a cyclic trimer with a macrocyclic 12-membered ring structure formed by the bidentate bridging coordination of carboxylate group to tin atoms. The tin atom is six-coordinated in a distorted octahedral geometry. In complex 2, the distorted trigonal bipyramidal Et2SnL2 units are linked into polymeric chains by the weak Sn…O interaction involving Sn and the earbonyl O of an adjacent ligand, and the chains are further connected by intermolecular N-H…O hydrogen bonds to form a two-dimensional supramolecular structure.展开更多
A new bicadmium(??) complex [Cd2L](ClO4)2?1.25H2O (C28H35Cd2Cl4N6O13.25) was synthesized and characterized by X-ray diffraction and ES mass spectral analyses. It crystallizes in the triclinic system, space gro...A new bicadmium(??) complex [Cd2L](ClO4)2?1.25H2O (C28H35Cd2Cl4N6O13.25) was synthesized and characterized by X-ray diffraction and ES mass spectral analyses. It crystallizes in the triclinic system, space group P1 with a = 15.630(3), b = 15.990(3), c = 16.330(3) ?, α = 89.90(3), β = 68.87(3), γ = 87.94(3)o, V = 3804.1(13) ?3, Mr = 1034.22, Z = 4, F(000) = 2060, Dc = 1.806 g/cm3, T = 293(2) K, μ = 1.468 mm-1 and λ = 0.71073 ?. The structure was refined to R = 0.0779 and wR = 0.1960 for 7034 observed reflections with I > 2σ(I).展开更多
Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic a...Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.展开更多
The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: ...The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.展开更多
A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)...A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.展开更多
One novel organic-inorganic hybrid supramolecular assemblies ｜（NDPA）（18-crown-6）]2＋（DMA）＋·3ClO4^-（1）,has been successfully constructed through the prominent strategies of crystal engineering（NDPA = N,...One novel organic-inorganic hybrid supramolecular assemblies ｜（NDPA）（18-crown-6）]2＋（DMA）＋·3ClO4^-（1）,has been successfully constructed through the prominent strategies of crystal engineering（NDPA = N,N-dimethyI-1,4-phenylenediamine,DMA = dimethylamine）,and characterized by IR,powder XRD and single crystal X-ray diffraction.In the structure,the supramolecular organic cations and inorganic ClO_4^- anions are arranged alternately and linked by N-O…H hydrogen bonds.It is worthy to note that the ClO_4^- are linked to form one-dimensional inorganic chain through strong NH…O hydrogen bonds along b-axis.There is no distinct dielectric anomaly in the temperaturedependent and frequency-dependent dielectric constant curves,suggesting that no phase transition exists within the measured temperature range（120-420 K）.The relative displacement of cations and anions,the turned polarization of molecular electric moment and macrocyclic molecule rotator are the main factors to determine the trend of dielectric constant.展开更多
A new binucleating macrocyclic ligand 2,6-bis (1,4,7,10-te-traazacyclododecan-10-ylmethyl)methoxy-benzene (L) and its binuclear copper (II) complex, [ Cu2LBr2 ] (ClO4 )2 · 3H2O (1), was prepared and the structur... A new binucleating macrocyclic ligand 2,6-bis (1,4,7,10-te-traazacyclododecan-10-ylmethyl)methoxy-benzene (L) and its binuclear copper (II) complex, [ Cu2LBr2 ] (ClO4 )2 · 3H2O (1), was prepared and the structure was determined by X-ray crystallography. Complex 1 crystallizes in monoclinic crystal system, P21/n space group with a = 0.8206(3), b = 2.0892(8), c = 2.3053(7) nm, β=95.83(2)°, V = 3.932 nm3, Mr = 1017.57, Z = 4, Dc= 1.692 g/cm3, and R = 0. 0489, Rw= 0.0552 for 6571 observed reflections with I≥2σ (I). Both of the copper(II) centers are coordinated by four amine nitrogen donors of cyclen subunits and a bromide an-ion, and each copper (II) ion is in a square-pyramidal coordination environment. Variable temperature magnetic susceptibility studies indicate that there exists weak intramolecular an-tiferro-magnetic coupling ( - 2J = 2.06 cm-1) between the two copper(n) centers.展开更多
A tetranuclear Mn(Ⅳ) complex \{\[L\-4Mn\-4O\-6\]\}(ClO\-4)\-4\52H\-2O (L=tacn)was synthesized from Mn(CH\-3COO)\-2\54H\-2O, tacn and NaClO\-4 and characterized by XRD. The compound crystallizes in monoclinic system, ...A tetranuclear Mn(Ⅳ) complex \{\[L\-4Mn\-4O\-6\]\}(ClO\-4)\-4\52H\-2O (L=tacn)was synthesized from Mn(CH\-3COO)\-2\54H\-2O, tacn and NaClO\-4 and characterized by XRD. The compound crystallizes in monoclinic system, space group P2\-1/n , with a =2.133 5(6) nm, b =1.138 7(3) nm, \{ c =\}\{2.178 8(6) nm\}, β =67.40(3)°, V =4.928(2) nm 3 , Z =4, R =0.062 0. Magnetic investigations reveal a weak ferromagnetic property with J =8.8 cm -1 .展开更多
The compound 2,4,4,9,11,11-hexamethyl-1,5,8,12-tetraazacyclotetradecane-1,8-diene(1) was synthesized by new method with high yield(95.2%),and its complex with Cu(II) and SCN-was also obtained.The structures of both th...The compound 2,4,4,9,11,11-hexamethyl-1,5,8,12-tetraazacyclotetradecane-1,8-diene(1) was synthesized by new method with high yield(95.2%),and its complex with Cu(II) and SCN-was also obtained.The structures of both the ligand and the complex were characterized by IR,elemental analysis,and X-ray diffraction.The crystal of the title compound(2) belongs to monoclinic system,space group P21/n,Mr=501.53,a=1.28883(11) nm,b=1.13462(10) nm,c=1.58128(13) nm,β=102.7430(10)°,V=2.2554(3) nm3,Z=4,d=1.477g/ cm3,F(000)=1052.R1=0.0360,wR2=0.0976[I>2σ(Ⅰ)].The copper atom is five–coordinated with four nitrogen atoms from compound 1 and one nitrogen atom from thiocyanate to form a tetragonal pyramid structure.展开更多
基金financial support from the National Natural Science Foundation of China (NSFC) (Nos. 21788102, 21722603 and 21871083)Project supported by Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03)+2 种基金the Innovation Program of Shanghai Municipal Education Commission (No. 2017-01-07-00-02-E00010)State Key Laboratory for Modification of Chemical Fibers and Polymer Materials (No. KF1803)Donghua University and the Fundamental Research Funds (No. KF1803) for the Central Universities
文摘Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem crossing(ISC) and suppressing non-radiative transitions. In supramolecular chemistry, the control and regulation of molecular recognition based on the role of the host and guest in supramolecular polymers matrix, has attracted much attention. Recently, researchers have successfully achieved room temperature phosphorescence of pure organic complexes through host-guest interactions. The host molecule specifically includes the phosphorescent guest to reduce non-radiative transitions and enhance room temperature phosphorescence emission. This review aims to describe the developments and achievements of pure organic room temperature phosphorescence systems through the mechanism of host-guest interactions in recent years, and demonstrates the exploration and pursuit of phosphorescent materials of researchers in different fields.
基金supported by the NNSFC (20701027)the Post-Doctor Innovation Project of Shandong Province (200702021) the Key Laboratory of Colloid Interface Chemistry of Ministry of Education (200707)
文摘Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-ray single-crystal diffraction analysis. Complex 1 belongs to the trigonal system, space group R-3 with a = b = 19.2730（5）, c = 23.6890（13）A^°, V= 7620.4（5） A^°^3, Z = 6, Dc= 1.553 g/cm^3,μ= 1.518 mm^-1, F（000） = 3600, R = 0.0238 and wR = 0.0636. Complex 2 is of monoelinie system, space group P21/c with a = 13.7550（8）, b = 11.5425（7）, c = 12.7876（7）A^°, β= 93.585（1）°, V = 2026.3（2） A^°^3, Z = 4, Dc= 1.548 g/cm^3,μ = 1.286 mm^-1, F（000） = 976, R = 0.0298 and wR = 0.0722. Complex 1 is a cyclic trimer with a macrocyclic 12-membered ring structure formed by the bidentate bridging coordination of carboxylate group to tin atoms. The tin atom is six-coordinated in a distorted octahedral geometry. In complex 2, the distorted trigonal bipyramidal Et2SnL2 units are linked into polymeric chains by the weak Sn…O interaction involving Sn and the earbonyl O of an adjacent ligand, and the chains are further connected by intermolecular N-H…O hydrogen bonds to form a two-dimensional supramolecular structure.
基金This project was supported by the National Natural Science Foundation of China(No.50372028)
文摘A new bicadmium(??) complex [Cd2L](ClO4)2?1.25H2O (C28H35Cd2Cl4N6O13.25) was synthesized and characterized by X-ray diffraction and ES mass spectral analyses. It crystallizes in the triclinic system, space group P1 with a = 15.630(3), b = 15.990(3), c = 16.330(3) ?, α = 89.90(3), β = 68.87(3), γ = 87.94(3)o, V = 3804.1(13) ?3, Mr = 1034.22, Z = 4, F(000) = 2060, Dc = 1.806 g/cm3, T = 293(2) K, μ = 1.468 mm-1 and λ = 0.71073 ?. The structure was refined to R = 0.0779 and wR = 0.1960 for 7034 observed reflections with I > 2σ(I).
基金theNationalNaturalScienceFoundationofChina (No .2 0 0 72 0 2 7)
文摘Two new 15-membered functionalized macrocycles, dioxo^polyazacycloalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhydride (DTPA=diethylenetriaminepentaacetic acid) with 1,2-diaminopropane, (15-DTPA-1,2-pn), or 1,2-diaminocyclohexane, (15-DTPA-1,2-cy). Their lanthanide complexes [Ln(15-DTPA-1,2-pn)(H 2O)] 2 [Ln=Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H 2O)] 2 [Ln=Eu (3), Gd (4)] were also prepared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state; each metal ion is nine-coordinated in a distorted tricapped-trigonal prism. In complex 4, the coexistence of two diastereoisomeric molecules in the crystal lattice was observed.
基金The project was supported by the funds of the Key Laboratory of Organic Syntheses of Jiangsu province(KJS01018) and Funds of Young Teacher of Suzhou University
文摘The nickel(Ⅱ)complex [Ni(teta){N(CN)2}2] (teta = 5,7,7,12,14,14-hexamehyl-1,4, 8,11-tetraazacyclotetradecane) was synthesized and its structure has been determined by single- crystal X-ray diffraction. Crystal data: C20H36N10Ni, monoclinic, space group P21/c, a = 9.632(2), b = 11.833(2), c = 10.613(2) ? b = 93.46(3), V = 1207.4(4) ?, Mr = 475.30, Z = 2, Dc = 1.307 g/cm3, F(000) = 508, m(MoKa) = 0.831 mm-1, R = 0.0446 and wR = 0.1274 for 2423 observed reflections with I > 2s(I). The center nickel ion is coordinated by six nitrogen atoms, four from the macrocyclic ligand teta and the other two from two dicyanamides. The dicyanamide is coordinated to the metal atoms as uni-dentate manner via nitrile nitrogen atom.
基金the Natural Science Foundation of Shandong Province(No.Y2 0 0 2 B0 6 )
文摘A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.
基金financially supported by the 973 Project(No. 2014CB848800)National Natural Science Foundation of China (Nos.21422101 and 21301029)+1 种基金Jiangsu Province NSF(Nos. BK20140056 and BK20130600)Program for NCET and Ph.D. Programs Foundation of Ministry of Education of China(No. 20130092120013)
文摘One novel organic-inorganic hybrid supramolecular assemblies ｜（NDPA）（18-crown-6）]2＋（DMA）＋·3ClO4^-（1）,has been successfully constructed through the prominent strategies of crystal engineering（NDPA = N,N-dimethyI-1,4-phenylenediamine,DMA = dimethylamine）,and characterized by IR,powder XRD and single crystal X-ray diffraction.In the structure,the supramolecular organic cations and inorganic ClO_4^- anions are arranged alternately and linked by N-O…H hydrogen bonds.It is worthy to note that the ClO_4^- are linked to form one-dimensional inorganic chain through strong NH…O hydrogen bonds along b-axis.There is no distinct dielectric anomaly in the temperaturedependent and frequency-dependent dielectric constant curves,suggesting that no phase transition exists within the measured temperature range（120-420 K）.The relative displacement of cations and anions,the turned polarization of molecular electric moment and macrocyclic molecule rotator are the main factors to determine the trend of dielectric constant.
基金Project supported by the National Natural Science Foundation of China (No. 19771022 and 29971019), the Natural Science Foundation of Tianjin and the Trans-Century Talents Training Program Foundation from the State Education Ministry of China to Bu, X. H.
文摘 A new binucleating macrocyclic ligand 2,6-bis (1,4,7,10-te-traazacyclododecan-10-ylmethyl)methoxy-benzene (L) and its binuclear copper (II) complex, [ Cu2LBr2 ] (ClO4 )2 · 3H2O (1), was prepared and the structure was determined by X-ray crystallography. Complex 1 crystallizes in monoclinic crystal system, P21/n space group with a = 0.8206(3), b = 2.0892(8), c = 2.3053(7) nm, β=95.83(2)°, V = 3.932 nm3, Mr = 1017.57, Z = 4, Dc= 1.692 g/cm3, and R = 0. 0489, Rw= 0.0552 for 6571 observed reflections with I≥2σ (I). Both of the copper(II) centers are coordinated by four amine nitrogen donors of cyclen subunits and a bromide an-ion, and each copper (II) ion is in a square-pyramidal coordination environment. Variable temperature magnetic susceptibility studies indicate that there exists weak intramolecular an-tiferro-magnetic coupling ( - 2J = 2.06 cm-1) between the two copper(n) centers.
文摘A tetranuclear Mn(Ⅳ) complex \{\[L\-4Mn\-4O\-6\]\}(ClO\-4)\-4\52H\-2O (L=tacn)was synthesized from Mn(CH\-3COO)\-2\54H\-2O, tacn and NaClO\-4 and characterized by XRD. The compound crystallizes in monoclinic system, space group P2\-1/n , with a =2.133 5(6) nm, b =1.138 7(3) nm, \{ c =\}\{2.178 8(6) nm\}, β =67.40(3)°, V =4.928(2) nm 3 , Z =4, R =0.062 0. Magnetic investigations reveal a weak ferromagnetic property with J =8.8 cm -1 .
文摘The compound 2,4,4,9,11,11-hexamethyl-1,5,8,12-tetraazacyclotetradecane-1,8-diene(1) was synthesized by new method with high yield(95.2%),and its complex with Cu(II) and SCN-was also obtained.The structures of both the ligand and the complex were characterized by IR,elemental analysis,and X-ray diffraction.The crystal of the title compound(2) belongs to monoclinic system,space group P21/n,Mr=501.53,a=1.28883(11) nm,b=1.13462(10) nm,c=1.58128(13) nm,β=102.7430(10)°,V=2.2554(3) nm3,Z=4,d=1.477g/ cm3,F(000)=1052.R1=0.0360,wR2=0.0976[I>2σ(Ⅰ)].The copper atom is five–coordinated with four nitrogen atoms from compound 1 and one nitrogen atom from thiocyanate to form a tetragonal pyramid structure.
