Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance...Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.展开更多
A novel supramolecular adduct 3(C 42H 42N 28O 14) 2·H 2O (1) was synthesized by mixing 2- and cucurbit uril in solution of hydrochloric acid. The crystal structure was determined by single crys...A novel supramolecular adduct 3(C 42H 42N 28O 14) 2·H 2O (1) was synthesized by mixing 2- and cucurbit uril in solution of hydrochloric acid. The crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system and space group F dd2 with cell dimensions: a=4.705 33 (5) nm, b=7.153 80 (6) nm, c= 1.894 61 (2) nm, Z=16, V=63.7744 (11) nm3, D c= 1.534 g/cm3, μ=3.007 mm -1, F(000)=29 120, R 1= 0.070 7, wR 2=0.169 2. In crystal, the cucurb uril molecules form two zig-zag chains.展开更多
A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and charact...A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.展开更多
The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 wi...The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.展开更多
A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compo...A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pccn, with a = 7.4886（11）, b = 11.9667（18）, c = 13.550（2） A, V= 1214.3（3） A3, Z = 4, Mr= 370.60, Dc = 2.027 mg/m3, F（000） = 728,μ （MoKa） = 1.829 mm^-1, the final R = 0.0243 and wR = 0.0591 for 1150 unique reflections with I 〉 2σ（I）. The cadmium（II） center in the title complex is coordinated with two oxygen and two nitrogen atoms from two bidentate chelated imidazole-4-carboxlate ligands together with two water molecules, giving a distorted octahedral coordination geometry. A one-dimensional hydrogen bonding chain is formed via intermolecular O-H...O hydrogen bonds, and such adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular framework. Complex 1 exhibits a fluorescent emission band at 290 nm （λex = 236 nm） in the solid state.展开更多
A novel supramolecular compound,{[2-（2-pyridyl）benzimidazoleH2]2·[BiCl6]·Cl},was synthesized by the hydrothermal reaction of o-phenylenediamine and α-pyridinecarboxylic acid with BiCl3 in 6.0 mol·L-1...A novel supramolecular compound,{[2-（2-pyridyl）benzimidazoleH2]2·[BiCl6]·Cl},was synthesized by the hydrothermal reaction of o-phenylenediamine and α-pyridinecarboxylic acid with BiCl3 in 6.0 mol·L-1 HCl solution,and characterized by elemental analysis,IR,X-ray single-crystal diffraction and photoluminescence spectroscopy.The crystal （C24H22N6Cl7Bi,Mr= 851.61） belongs to the triclinic system,space group P1 with a =7.2887（18）,b =9.548（2）,c= 12.469（3）,α=85.306（4）,β=82.814（4）,γ=71.349（4）°,Z=1,V=814.9（3）3,Dc=1.735 g/cm3,μ（MoKα）=6.007 mm-1,F（000）=410,R=0.0307 and wR=0.0787.The bismuth ion and six chlorine ions construct a distorted octahedral configuration.The three-dimensional supramolecular network is built from electrostatic attractions,hydrogen bonds and π-π interaction between the BiCl6 anion,Cl anion and [2-（2-pyridyl）benzimidazoleH2] cation.The photoluminescence spectroscopy study shows that the title compound has a blue fluorescent emission at 450 nm in the solid state.展开更多
A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,el...A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy.The complex crystallizes in monoclinic,space group P21/c with a = 13.416（3）,b = 14.065（3）,c = 16.845（3）（A°） ,β = 110.55（3）o,V = 2976.5（10）（A°）^3,Z = 2,Dc = 1.796 g/cm^3,F（000） = 1564,GOOF = 0.962,the final R = 0.0686 and wR = 0.1746.The crystal structure shows that the lead ion is coordinated with two carboxylate O atoms from the 4-NBA anion,and four N atoms from two phen molecules,forming a slightly distorted pentagonalbipyramidal coordination geometry.It is further extended by various supramo-lecular interactions to form a three-dimensional supramolecular network.The TG analysis result shows that this complex begins decomposing at 30 ℃ and decompounding completely at 733 ℃.展开更多
A Ni（Ⅱ） supramolecular complex,[Ni 2 （btec）（3py） 2 （H 2 O） 8 ]（H 2 O） 4 （1）,has been synthesized by Ni（ClO 4） 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid （H 4 btec） and terminal ligand 3-hydro...A Ni（Ⅱ） supramolecular complex,[Ni 2 （btec）（3py） 2 （H 2 O） 8 ]（H 2 O） 4 （1）,has been synthesized by Ni（ClO 4） 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid （H 4 btec） and terminal ligand 3-hydroxypyridine （3py） in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637（12）,b=9.4138（13）,c=10.3611（14）,α=67.9540（10）,β=85.1740（10）,γ=76.9890（10）°,V=754.33（18） 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F（000）=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I 2σ（Ⅰ）.The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.展开更多
The compound [Cd（phen）（NCS）（SCN）]n（phen = 1,10-phenanthroline） was synthe- sized under hydrothermal conditions and characterized by IR and single-crystal X-ray diffraction. The complex is of monoclinic, space ...The compound [Cd（phen）（NCS）（SCN）]n（phen = 1,10-phenanthroline） was synthe- sized under hydrothermal conditions and characterized by IR and single-crystal X-ray diffraction. The complex is of monoclinic, space group C2/c with a = 14.607（3）, b = 10.505（2）, c = 10.631（2）A,β = 115.14（3）^o, V = 1476.8（5）A^3, C14H8CdN4S2, Mr = 408.76, Z = 4, F（000） = 800, μ = 1.757 mm^-1 and Dc = 1.839 g/cm^3. The final R = 0.0409 and wR = 0.0811 for 1367 observed reflections （I 〉 2σ（I））. In the title compound, each cadmium atom is six-coordinated and connected with two adjacent metal ions by two NCS bridges, creating a zigzag chain. The neighboring chains are linked to each other by the weak van der Waals＇ S…S interactions and π…π interactions to form a new three-dimensional supramolecular framework.展开更多
A novel binucleus complex [Cd2（phen）4（adip）（NO3）2] （phen = phenanthroline, H2adip = adipic acid） has been synthesized by the reaction of phen and H2adip with cadmium（Ⅱ） salt. Elemental analysis, IR spectra ...A novel binucleus complex [Cd2（phen）4（adip）（NO3）2] （phen = phenanthroline, H2adip = adipic acid） has been synthesized by the reaction of phen and H2adip with cadmium（Ⅱ） salt. Elemental analysis, IR spectra and X-ray crystal structure analysis were carried out to determine the crystal structure of the title complex. The crystal belongs to triclinic, space group P1^- with a = 9.638（7）, b = 10.315（7）, c = 13.109（10） A, α = 88.305（11）, β = 69.011（11）, γ = 75.818（11）°, C27H20N5O5Cd, Mr = 606.88, Z = 2, V = 1177.2（14）A^3, Dc = 1.712 g/cm^3,μ= 0.979 mm^-1, -8≤h ≤11, -12≤k≤ 12, -10≤l≤ 15, F（000） = 610, Rint = 0.0314, R = 0.0739 and wR = 0.1922 （Ⅰ〉 2σ（Ⅰ）. The cadmium atom is seven-coordinated in a distorted pentagonal bipyramidal configuration. The complex forms a 2-D supramolecular framework by C-H…O weak interactions and π-π stacking of neighbouring phen ligands.展开更多
A new bis（imidazolium） compound,[H2L（H2btec）2]·H4btec（1,L=1,1＇-（butane-1,4-diyl）bis（imidazole）,H4btec=1,2,4,5-benzenetetracarboxylatic acid）,has been synthesized and structurally characterized by singl...A new bis（imidazolium） compound,[H2L（H2btec）2]·H4btec（1,L=1,1＇-（butane-1,4-diyl）bis（imidazole）,H4btec=1,2,4,5-benzenetetracarboxylatic acid）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The title compound crystallizes in the monoclinic system,space group Pnma,with a=13.3908（11）,b=13.9249（12）,c=16.2166（14）,V=2957.6（4）3,Z=4,Mr=698.55,Dc=1.569 mg/m3,F（000）=1448,μ（MoKα）=0.130 mm-1,the final R=0.0584 and wR=0.1538 for 4295 observed reflections with I2σ（I）.The compound consists of one 1,1＇-（butane-1,4-diyl）bis（imidazolium） cation,one neutral H4btec and one H2btec2-（Only two para carboxyl groups are deprotonated,and two protonated ones remain free） anion.A one-dimensional hydrogen bonding chain and a 2D hydrogen bonding network are formed via intermolecular N–H…O and O–H…O hydrogen bonds.These adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular network.展开更多
The title compound {[Cu4（OH）4（2,2＇-bpy）4（bqdc）]·2ClO4}n 1 （bqdc = 2,2＇-biquinoline-4,4＇-dicarboxylic acid） has been synthesized by hydrothermal method. Its crystal structure is of triclinic, space grou...The title compound {[Cu4（OH）4（2,2＇-bpy）4（bqdc）]·2ClO4}n 1 （bqdc = 2,2＇-biquinoline-4,4＇-dicarboxylic acid） has been synthesized by hydrothermal method. Its crystal structure is of triclinic, space group P1^- with a = 7.6561（5）, b = 12.4652（8）, c = 15.7501（10） A, α= 80.0480（10）, β= 87.7900（10）, γ = 74.0800（1）°, V = 1423.65（16） A^3, Z = 2, C30H23ClN5O8Cu2, Mr = 744.06, Dc = 1.736 g/cm^3, μ = 1.651 mm^-1, F（000） = 754, the final R = 0.0421 and wR = 0.1163 for 4973 observed reflections with Ⅰ〉 2σ（Ⅰ）. In 1, tetra-copper chair-like clusters of [Cu4（OH）4（2,2＇-bpy）4]^4＋ are connected by bqdc ligands to form one-dimensional chains, which are further connected by hydrogen bonds to generate a two-dimensional supramolecular network .展开更多
The supramolecular compound [(AgI3)(4-HBPFA)2(H2O)] (Mr = 1361.11) was synthesized via the reaction of 1,1?-bis[(4-pyridylamino)carbonyl]ferrocene (4-BPFA) with AgI, and structurally characterized by single-crystal X-...The supramolecular compound [(AgI3)(4-HBPFA)2(H2O)] (Mr = 1361.11) was synthesized via the reaction of 1,1?-bis[(4-pyridylamino)carbonyl]ferrocene (4-BPFA) with AgI, and structurally characterized by single-crystal X-ray diffraction analysis. Crystal data: monoclinic, space group C2/c, a = 1.6783(3), b = 10.646(2), c = 2.5419(5) ?, β = 93.66(3)o, V = 4532.2(16) ?3, Z = 4, Dc = 1.995 g/cm3, F(000) = 2632 and μ = 3.158 mm-1. The compound consists of (4- HBPFA)+, (AgI3)2- and H2O. In the structure, the adjacent (4-HBPFA)+ are linked by C–H…O and N–H…N hydrogen bonds into 1-D chains which are further linked by C–H…I and N–H…I hydrogen bonds as well as intermolecular π-π stacking interactions to form a 3-D supramolecular compound.展开更多
A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （t...A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （tris（hydroxymethyl）aminomethane） and H2O in the molar ratio of 3：1：1：0.5：2.5：1400. Compound 1 crystallizes in the space group P42212 of the tetragonal system with a = b = 21.5009（8）, c = 28.401（2） A, V= 13129.5（12） A^3 Z = 4, Dc = 1.800 g/cm^3, μ（MoKa） = 1.932 mm^-1, λ（MoKa） = 0.71073 A, F（000） = 7063.4, C120H81.20ClCu5N20O38.7V15.35, Mr = 3557.58, the final R = 0.0594 and wR= 0.1320 for 7761 observed reflections （I 〉 2σ（I））. Structure analysis shows that 1 exhibits a 3D channel framework formed by the supramolecular assembly of Cu complexes and polyoxovanadate clusters via intermolecular hydrogen bonding, and the channels contain Cu complexes. Other characterizations by elemental analysis, XPS, IR, XRD and thermal analysis are also described.展开更多
The reactions of SbCl3 and HgCl2 with 2-（3-pyridyl）benzimidazole （PyBIm） in solution acidified with HCl have been investigated. The PyBIm ligands are protonated into 2-（3-pyridinio）benzimidazolium （H2PyBIm） ca...The reactions of SbCl3 and HgCl2 with 2-（3-pyridyl）benzimidazole （PyBIm） in solution acidified with HCl have been investigated. The PyBIm ligands are protonated into 2-（3-pyridinio）benzimidazolium （H2PyBIm） cations and the corresponding metal ions are bonded with chloride atoms into coordination anions, forming two new coordination compounds, namely, （H2PyBIm）（SbCl5） 1 and （H2PyBIm）2（Hg2Cl8） 2. Both compounds were characterized by X-ray crystallography. Crystal data for 1： triclinic, space group P1^- with a = 5.7030（7）, b = 9.0625（11）, c = 16.5929（18） A, α = 91.808（7）°, β = 93.234（6）, γ = 99.216（7）°, C12H11N3SbCl5, Mr = 496.24, V = 844.44（17） A^3, Z = 2, Dc = 1.952 g/cm^3, μ（MoKα） = 2.419 mm^-1, F（000） = 480, the final R = 0.0496 and wR = 0.1382 for 3433 observed reflections （I 〉 2σ（I））. Crystal data for 2： monoclinic, space group P21/c with a = 7.8061（5）, b = 15.8127（9）, c = 12.2435（9） , β = 91.955（4）o, C24H22N6Hg2Cl8, Mr = 1079.26, V = 1510.40（17） 3, Z = 2, Dc = 2.373 g/cm3, μ（MoKα） = 10.889 mm-1, F（000） = 1008, the final R = 0.0293 and wR = 0.0562 for 2854 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that the antimony（III） is five-coordinated, exhibiting a slightly distorted square-pyramidal coordination geometry; while in 2, a dimeric [Hg2Cl8]^4-anion consists of two trigonal bipyramids sharing two common edges. The organic cations and coordination anions are connected into a one-dimensional belt and a two-dimensional sheet through N-H···Cl hydrogen bonding interactions in compounds 1 and 2, respectively; both are further aggregated into 3D frameworks by strong π-π contacts.展开更多
The title compounds, [Co（H2O）6]（OVA）2·2H2O 1, [Ni（H2O）6]（OVA）2·2H2O 2 and [Zn（OVA）2·2H2O] 3 （HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate）, were synthesized and characterized by sing...The title compounds, [Co（H2O）6]（OVA）2·2H2O 1, [Ni（H2O）6]（OVA）2·2H2O 2 and [Zn（OVA）2·2H2O] 3 （HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate）, were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. Compounds 1 and 2 are both of triclinic with space group P1. The metal atom coordinated by six water molecules displays a slightly distorted octahedral configuration. Interestingly, the carboxyl group from HOVA ligand does not coordinate to the metal atom. Correspondingly, compound 3 belongs to the monoclinic system, space group C2/c. Each zinc（Ⅱ） atom exhibits a distorted four-coordinated tetrahedral geometry. Two monodentate carboxyl groups link one zinc（Ⅱ） atom to form a mononuclear molecule. The structure feature is different from that of compounds 1 and 2, which could be attributed to the different coordinated numbers and radii of Co（Ⅱ）, Ni（Ⅱ） and Zn（Ⅱ） atoms.展开更多
The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR ...The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.展开更多
A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and elec...A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146（6）, b=1.2581（8）, c=2.2316（14） nm, α=99.352（10）,β=97.209（9）, γ=103.935（9）°, V=2.422（3） nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F（000）=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections （I 〉 2σ（I））. In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.展开更多
The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric ...The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric unit consists of a [Mn（pmta_）3]ˉ anion, half [Mn（H_2O）_6]^（2＋） counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.展开更多
文摘Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.
文摘A novel supramolecular adduct 3(C 42H 42N 28O 14) 2·H 2O (1) was synthesized by mixing 2- and cucurbit uril in solution of hydrochloric acid. The crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system and space group F dd2 with cell dimensions: a=4.705 33 (5) nm, b=7.153 80 (6) nm, c= 1.894 61 (2) nm, Z=16, V=63.7744 (11) nm3, D c= 1.534 g/cm3, μ=3.007 mm -1, F(000)=29 120, R 1= 0.070 7, wR 2=0.169 2. In crystal, the cucurb uril molecules form two zig-zag chains.
基金Supported by the National Natural Science Foundation of China (Nos. 20971065, 20721002)National Basic Research Program of China (2007CB925103,2010CB923303)
文摘Four cobalt supramolecular architectures with Hmtyaa（2-（5-methyl-1,3,4-thiadiazol-2-ylthio）acetic acid） ligand have been synthesized.[Co（mtyaa）2（H2O）4]·4（H2O）（1）：triclinic,space group P1 with a = 6.7537（18）,b = 8.591（2）,c = 10.615（3） ,α = 96.495（4）,β = 99.955（5）,γ = 103.615（5）°,V = 581.9（3） 3,Z = 1,Mr = 581.52,Dc = 1.659 g/m3,μ = 1.158 mm-1,F（000） = 301,Rint = 0.0557,R = 0.0377 and wR = 0.1056 for 1854 observed reflections with Ⅰ 〉 2σ（Ⅰ）;{[Co（4,4＇-bipy）（H2O）4]·2（mtyaa）·2（H2O）}n（2）：triclinic,space group P1 with a = 7.669（2）,b = 8.840（3）,c = 11.521（4） ,α = 79.912（5）,β = 73.954（5）,γ = 86.612（6）°,V = 738.9（4） 3,Z = 1,Mr = 701.67,Dc = 1.577 g/m3,μ = 0.924 mm-1,F（000） = 363,Rint = 0.0636,R = 0.0498 and wR = 0.1311 for 2155 observed reflections with Ⅰ 〉 2σ（Ⅰ）;{[Co（4,4＇-bipy）（mtyaa）（H2O）3]（mtyaa）·2（H2O）}（3）：monoclinic,space group Pc with a = 7.7832（17）,b = 11.527（3）,c = 31.483（7） ,β = 91.952（4）°,V = 2822.9（11） 3,Z = 4,Mr = 683.65,Dc = 1.609 g/m3,μ = 0.963 mm-1,F（000） = 1412,Rint = 0.0758,R = 0.0609 and wR = 0.1095 for 5841 observed reflections with I 〉 2σ（I）;{[Co（bpe）（mtyaa）2（H2O）2]}n（4）：monoclinic,space group C2/c with a = 19.290（11）,b = 12.027（7）,c = 14.865（8） ,β = 125.648（8）°,V = 2802（3）3,Z = 4,Mr = 657.66,Dc = 1.559 g/m3,μ = 0.959 mm-1,F（000） = 1356,Rint = 0.0456,R = 0.0332 and wR = 0.0985 for 2299 observed reflections with Ⅰ 〉 2σ（Ⅰ）.
基金Supported by the Natural Science Foundation of Henan Province (No. 0611023700)Natural Science Foundation of Education Department of Henan Province (No. 2006150019)
文摘A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.
基金the Education Department of Jiangxi Province (No. 2007-125)the Initial Fund for Doctors from Jiangxi Normal University
文摘The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.
基金supported by the Natural Science Foundation of Henan Province (No.0511022600)the Department of Education of Henan Province (No.200510482006)
文摘A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pccn, with a = 7.4886（11）, b = 11.9667（18）, c = 13.550（2） A, V= 1214.3（3） A3, Z = 4, Mr= 370.60, Dc = 2.027 mg/m3, F（000） = 728,μ （MoKa） = 1.829 mm^-1, the final R = 0.0243 and wR = 0.0591 for 1150 unique reflections with I 〉 2σ（I）. The cadmium（II） center in the title complex is coordinated with two oxygen and two nitrogen atoms from two bidentate chelated imidazole-4-carboxlate ligands together with two water molecules, giving a distorted octahedral coordination geometry. A one-dimensional hydrogen bonding chain is formed via intermolecular O-H...O hydrogen bonds, and such adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular framework. Complex 1 exhibits a fluorescent emission band at 290 nm （λex = 236 nm） in the solid state.
基金Supported by the Natural Science Foundation of Henan Province (No. 0611023700)
文摘A novel supramolecular compound,{[2-（2-pyridyl）benzimidazoleH2]2·[BiCl6]·Cl},was synthesized by the hydrothermal reaction of o-phenylenediamine and α-pyridinecarboxylic acid with BiCl3 in 6.0 mol·L-1 HCl solution,and characterized by elemental analysis,IR,X-ray single-crystal diffraction and photoluminescence spectroscopy.The crystal （C24H22N6Cl7Bi,Mr= 851.61） belongs to the triclinic system,space group P1 with a =7.2887（18）,b =9.548（2）,c= 12.469（3）,α=85.306（4）,β=82.814（4）,γ=71.349（4）°,Z=1,V=814.9（3）3,Dc=1.735 g/cm3,μ（MoKα）=6.007 mm-1,F（000）=410,R=0.0307 and wR=0.0787.The bismuth ion and six chlorine ions construct a distorted octahedral configuration.The three-dimensional supramolecular network is built from electrostatic attractions,hydrogen bonds and π-π interaction between the BiCl6 anion,Cl anion and [2-（2-pyridyl）benzimidazoleH2] cation.The photoluminescence spectroscopy study shows that the title compound has a blue fluorescent emission at 450 nm in the solid state.
基金supported by the National Natural Science Foundation of China (No. 20947003)China Postdoctoral Science Foundation (No. 20090461066)
文摘A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy.The complex crystallizes in monoclinic,space group P21/c with a = 13.416（3）,b = 14.065（3）,c = 16.845（3）（A°） ,β = 110.55（3）o,V = 2976.5（10）（A°）^3,Z = 2,Dc = 1.796 g/cm^3,F（000） = 1564,GOOF = 0.962,the final R = 0.0686 and wR = 0.1746.The crystal structure shows that the lead ion is coordinated with two carboxylate O atoms from the 4-NBA anion,and four N atoms from two phen molecules,forming a slightly distorted pentagonalbipyramidal coordination geometry.It is further extended by various supramo-lecular interactions to form a three-dimensional supramolecular network.The TG analysis result shows that this complex begins decomposing at 30 ℃ and decompounding completely at 733 ℃.
基金supported by the Natural Science Foundation of Henan Province (Nos. 092102310075 and 0511022600)
文摘A Ni（Ⅱ） supramolecular complex,[Ni 2 （btec）（3py） 2 （H 2 O） 8 ]（H 2 O） 4 （1）,has been synthesized by Ni（ClO 4） 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid （H 4 btec） and terminal ligand 3-hydroxypyridine （3py） in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637（12）,b=9.4138（13）,c=10.3611（14）,α=67.9540（10）,β=85.1740（10）,γ=76.9890（10）°,V=754.33（18） 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F（000）=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I 2σ（Ⅰ）.The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.
基金This work was supported by the State Key Laboratory of Structural Chemistry the Young Talent Programmed of Fujian Province (No. 2006F3072)
文摘The compound [Cd（phen）（NCS）（SCN）]n（phen = 1,10-phenanthroline） was synthe- sized under hydrothermal conditions and characterized by IR and single-crystal X-ray diffraction. The complex is of monoclinic, space group C2/c with a = 14.607（3）, b = 10.505（2）, c = 10.631（2）A,β = 115.14（3）^o, V = 1476.8（5）A^3, C14H8CdN4S2, Mr = 408.76, Z = 4, F（000） = 800, μ = 1.757 mm^-1 and Dc = 1.839 g/cm^3. The final R = 0.0409 and wR = 0.0811 for 1367 observed reflections （I 〉 2σ（I））. In the title compound, each cadmium atom is six-coordinated and connected with two adjacent metal ions by two NCS bridges, creating a zigzag chain. The neighboring chains are linked to each other by the weak van der Waals＇ S…S interactions and π…π interactions to form a new three-dimensional supramolecular framework.
基金This work was supported by the Foundation of Education Committee of Liaoning Province (No. 2004c021) and Foundation of Excellent Personal of Shenyang Institute of Chemical Technology
文摘A novel binucleus complex [Cd2（phen）4（adip）（NO3）2] （phen = phenanthroline, H2adip = adipic acid） has been synthesized by the reaction of phen and H2adip with cadmium（Ⅱ） salt. Elemental analysis, IR spectra and X-ray crystal structure analysis were carried out to determine the crystal structure of the title complex. The crystal belongs to triclinic, space group P1^- with a = 9.638（7）, b = 10.315（7）, c = 13.109（10） A, α = 88.305（11）, β = 69.011（11）, γ = 75.818（11）°, C27H20N5O5Cd, Mr = 606.88, Z = 2, V = 1177.2（14）A^3, Dc = 1.712 g/cm^3,μ= 0.979 mm^-1, -8≤h ≤11, -12≤k≤ 12, -10≤l≤ 15, F（000） = 610, Rint = 0.0314, R = 0.0739 and wR = 0.1922 （Ⅰ〉 2σ（Ⅰ）. The cadmium atom is seven-coordinated in a distorted pentagonal bipyramidal configuration. The complex forms a 2-D supramolecular framework by C-H…O weak interactions and π-π stacking of neighbouring phen ligands.
基金supported by the Natural Science Foundation of Henan Province (No 092102310075)
文摘A new bis（imidazolium） compound,[H2L（H2btec）2]·H4btec（1,L=1,1＇-（butane-1,4-diyl）bis（imidazole）,H4btec=1,2,4,5-benzenetetracarboxylatic acid）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The title compound crystallizes in the monoclinic system,space group Pnma,with a=13.3908（11）,b=13.9249（12）,c=16.2166（14）,V=2957.6（4）3,Z=4,Mr=698.55,Dc=1.569 mg/m3,F（000）=1448,μ（MoKα）=0.130 mm-1,the final R=0.0584 and wR=0.1538 for 4295 observed reflections with I2σ（I）.The compound consists of one 1,1＇-（butane-1,4-diyl）bis（imidazolium） cation,one neutral H4btec and one H2btec2-（Only two para carboxyl groups are deprotonated,and two protonated ones remain free） anion.A one-dimensional hydrogen bonding chain and a 2D hydrogen bonding network are formed via intermolecular N–H…O and O–H…O hydrogen bonds.These adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular network.
基金This work was supported by the National Natural Science Foundation of China (20571074)Natural Science Foundation of Fujian Province
文摘The title compound {[Cu4（OH）4（2,2＇-bpy）4（bqdc）]·2ClO4}n 1 （bqdc = 2,2＇-biquinoline-4,4＇-dicarboxylic acid） has been synthesized by hydrothermal method. Its crystal structure is of triclinic, space group P1^- with a = 7.6561（5）, b = 12.4652（8）, c = 15.7501（10） A, α= 80.0480（10）, β= 87.7900（10）, γ = 74.0800（1）°, V = 1423.65（16） A^3, Z = 2, C30H23ClN5O8Cu2, Mr = 744.06, Dc = 1.736 g/cm^3, μ = 1.651 mm^-1, F（000） = 754, the final R = 0.0421 and wR = 0.1163 for 4973 observed reflections with Ⅰ〉 2σ（Ⅰ）. In 1, tetra-copper chair-like clusters of [Cu4（OH）4（2,2＇-bpy）4]^4＋ are connected by bqdc ligands to form one-dimensional chains, which are further connected by hydrogen bonds to generate a two-dimensional supramolecular network .
基金This work was supported by the Outstanding Young Foundation of Henan Province
文摘The supramolecular compound [(AgI3)(4-HBPFA)2(H2O)] (Mr = 1361.11) was synthesized via the reaction of 1,1?-bis[(4-pyridylamino)carbonyl]ferrocene (4-BPFA) with AgI, and structurally characterized by single-crystal X-ray diffraction analysis. Crystal data: monoclinic, space group C2/c, a = 1.6783(3), b = 10.646(2), c = 2.5419(5) ?, β = 93.66(3)o, V = 4532.2(16) ?3, Z = 4, Dc = 1.995 g/cm3, F(000) = 2632 and μ = 3.158 mm-1. The compound consists of (4- HBPFA)+, (AgI3)2- and H2O. In the structure, the adjacent (4-HBPFA)+ are linked by C–H…O and N–H…N hydrogen bonds into 1-D chains which are further linked by C–H…I and N–H…I hydrogen bonds as well as intermolecular π-π stacking interactions to form a 3-D supramolecular compound.
基金This work was supported by the National Natural Science Foundation of China (No. 20271011)
文摘A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （tris（hydroxymethyl）aminomethane） and H2O in the molar ratio of 3：1：1：0.5：2.5：1400. Compound 1 crystallizes in the space group P42212 of the tetragonal system with a = b = 21.5009（8）, c = 28.401（2） A, V= 13129.5（12） A^3 Z = 4, Dc = 1.800 g/cm^3, μ（MoKa） = 1.932 mm^-1, λ（MoKa） = 0.71073 A, F（000） = 7063.4, C120H81.20ClCu5N20O38.7V15.35, Mr = 3557.58, the final R = 0.0594 and wR= 0.1320 for 7761 observed reflections （I 〉 2σ（I））. Structure analysis shows that 1 exhibits a 3D channel framework formed by the supramolecular assembly of Cu complexes and polyoxovanadate clusters via intermolecular hydrogen bonding, and the channels contain Cu complexes. Other characterizations by elemental analysis, XPS, IR, XRD and thermal analysis are also described.
基金supported by the Natural Science Foundation of Fujian Province (2007HZ0001-1, 2009HZ0004-1, 2009HZ0006-1 and 2006L2005)
文摘The reactions of SbCl3 and HgCl2 with 2-（3-pyridyl）benzimidazole （PyBIm） in solution acidified with HCl have been investigated. The PyBIm ligands are protonated into 2-（3-pyridinio）benzimidazolium （H2PyBIm） cations and the corresponding metal ions are bonded with chloride atoms into coordination anions, forming two new coordination compounds, namely, （H2PyBIm）（SbCl5） 1 and （H2PyBIm）2（Hg2Cl8） 2. Both compounds were characterized by X-ray crystallography. Crystal data for 1： triclinic, space group P1^- with a = 5.7030（7）, b = 9.0625（11）, c = 16.5929（18） A, α = 91.808（7）°, β = 93.234（6）, γ = 99.216（7）°, C12H11N3SbCl5, Mr = 496.24, V = 844.44（17） A^3, Z = 2, Dc = 1.952 g/cm^3, μ（MoKα） = 2.419 mm^-1, F（000） = 480, the final R = 0.0496 and wR = 0.1382 for 3433 observed reflections （I 〉 2σ（I））. Crystal data for 2： monoclinic, space group P21/c with a = 7.8061（5）, b = 15.8127（9）, c = 12.2435（9） , β = 91.955（4）o, C24H22N6Hg2Cl8, Mr = 1079.26, V = 1510.40（17） 3, Z = 2, Dc = 2.373 g/cm3, μ（MoKα） = 10.889 mm-1, F（000） = 1008, the final R = 0.0293 and wR = 0.0562 for 2854 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that the antimony（III） is five-coordinated, exhibiting a slightly distorted square-pyramidal coordination geometry; while in 2, a dimeric [Hg2Cl8]^4-anion consists of two trigonal bipyramids sharing two common edges. The organic cations and coordination anions are connected into a one-dimensional belt and a two-dimensional sheet through N-H···Cl hydrogen bonding interactions in compounds 1 and 2, respectively; both are further aggregated into 3D frameworks by strong π-π contacts.
基金supported by the National Natural Science Foundation of China (No. 20573073)the Natural Scientific Research Foundation of Shaanxi Provincial Education Office of China (No. 09JK826, 08JZ82 and 08JK490)
文摘The title compounds, [Co（H2O）6]（OVA）2·2H2O 1, [Ni（H2O）6]（OVA）2·2H2O 2 and [Zn（OVA）2·2H2O] 3 （HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate）, were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. Compounds 1 and 2 are both of triclinic with space group P1. The metal atom coordinated by six water molecules displays a slightly distorted octahedral configuration. Interestingly, the carboxyl group from HOVA ligand does not coordinate to the metal atom. Correspondingly, compound 3 belongs to the monoclinic system, space group C2/c. Each zinc（Ⅱ） atom exhibits a distorted four-coordinated tetrahedral geometry. Two monodentate carboxyl groups link one zinc（Ⅱ） atom to form a mononuclear molecule. The structure feature is different from that of compounds 1 and 2, which could be attributed to the different coordinated numbers and radii of Co（Ⅱ）, Ni（Ⅱ） and Zn（Ⅱ） atoms.
文摘The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.
基金This work was supported by the National Natural Science Foundation of China (No. 20401008)
文摘A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146（6）, b=1.2581（8）, c=2.2316（14） nm, α=99.352（10）,β=97.209（9）, γ=103.935（9）°, V=2.422（3） nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F（000）=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections （I 〉 2σ（I））. In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.
基金supported by the National Natural Science Foundation of China(No.20801012)New Energy Technology Co.Ltd.of Ai Naji of Jiangsu Province(No.8507040091)
文摘The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric unit consists of a [Mn（pmta_）3]ˉ anion, half [Mn（H_2O）_6]^（2＋） counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.
