Tetrameric(Bi_4I_(16))~(4-) Iodobismuthate Templated by 1,ω-Bis(isoquinoline)alkane Cation: Structure,Photoluminescence and Enhanced Thermochromism

Using 1,1?-bis(isoquinoline)-1,4-phenyldimethylenyl(BIQPM2+) cation as template, a new tetrameric(Bi4 I16)4-iodobismuthate-containing hybrid with formula of(BIQPM)2(Bi4 I16)·H2 O(1), has been prepared under solvothermal conditions. The centrosymmetric Bi4-4 I16 tetraanion is constructed from four edge-shared slightly distorted BiI6 octahedrons. Due to the presence of larger conjugated system(isoquinoline ring), strong π···π stacking interactions can be observed. Besides, strong I···I interactions can be monitored and extends the 0-D Bi4 I4-16 cluster to a quasi-1-D chain. The smaller energy gap of 2.13 eV is led by these non-covalent interactions. Its infrared emission might be caused by strong charge transfer between anions and cations. Furthermore, the reversible thermochromic behavior with low chromotropic temperature of 80 ℃ can be observed, whose mechanism was discussed.     

Ethoxycarbonylmethyl Viologen Induced Metal Halide-based Hybrids: Structures,Photoluminescence and Photocurrent Response Behavior

Two new ethoxycarbonylmethyl viologen induced metal halide-based hybrids,(Ae V)_2(Bi_4I_(16))(DMF)_2(1)and(Ae V)(CoCl_4)(2)(AeV~(2+)=N,N?-bis(ethoxycarbonylmethyl)-4,4?-bipyridinium)have been synthesized and structurally determined by X-ray diffraction method.Under the direction of a new template AeV~(2+),the(Bi_4I_(16))~(4-)tetramer constructed from four edge-sharing BiI_6octahedra(for 1)and(CoCl_4)~(2-)mono-nuclear(for 2)were obtained.Furthermore,C–H···O and C–H···X(X=I,Cl)hydrogen bonds contribute to the extension of structures from 0-D to 1-D chains.Their energy band gaps of 2.18 and 2.41 eV indicate their semiconductor properties,and the photoluminescence was detected on 1.Interestingly,2 exhibits good photocurrent response behavior.Electronic structure analysis was executed to correlate the structure/property.     

Quasi-3-D Gadolinium Iodate Constructed from Infinite Polyiodate: Structure,Green-emission and UV Light-driven Degradation on Organic Dye

A new gadolinium iodate has been synthesized via hydrothermal method, and its structure was determined as [Gd(H_2O)(IO_3)_2(IO_3H_2O)]_n(1) by X-ray single-crystal diffraction. The 2-D layer is built from the linkage of Gd_2O_(16)I_4 dimer via μ_2/μ_3-bridged iodates, and the quasi-3-D network is generated via weak I···O bonds and hydrogen bonds. FTIR, powder X-ray diffraction(PXRD) and UV-Vis spectra were conducted to characterize the as-synthesized sample. Interestingly, 1 exhibits green emission, which might be assigned to electronic transfer within iodate groups. The UV adsorption of 1 hints its UV light-driven photocatalytic property, and as expected, it exhibits photocatalytic activity for the degradation of rhodamine B. Theoretical calculation was conducted to give structure/property correlation.     

Study on Interaction of L-Tryptophan with p-Suffonatocalix[4]arene by Spectrofluorometry

The interactions between L-tryptophan（L-Trp） and water-soluble p-sulfonatocalix[4]- arene （SCX4） were investigated by spectrofluorometry. The effect of pH was discussed. The interaction process was estimated from the thermodynamic viewpoint. The SCX4 was found to be able to adjust its conformation to fit the size of L-Trp, and the benzene of L-Trp penetrated into the hydrophobic cavity of SCX4. Meanwhile, the binding mechanism was further elucidated by IHNMR and molecular mechanics calculations.     

Haloplumbate Nanochains Templated by Quaternary Phosphorus: Good Water Stabilities,Thermochromic Luminescence and Photocurrent Responses

Two triphenylmethylphosphonium/haloplumbate hybrids,i.e.,[(PPh_3Me)_2(Pb_2I_6)·CH_3CN]_n(1) and[(PPh_3Me)(PbBr_3)]_n(2),have been prepared,in which the(PbX_3)_n~(n-) nanochains built from face-sharing PbX_6 octahedra are surrounded by organic templates to assemble the core-shell quantum well.Besides,C-H…πinteractions among Ph_3 PMe~+ cations can also be detected,which give rise to the 2-D organic layer of 1 and 1-D chain for 2.The good water stabilities could be induced by the strong C-H…π interactions,which can deter the hydrolysis reaction.The energy band gaps of this work mainly derive from the charge transfer of organic components,but their luminescence stems from the inorganic(PbX_3)_n~(n-) nanochains with co-existence of free excitons and self-trapped excitons.At temperature lower than 117 K,strong quantum confinement will rule out the free excitons,and self-trapped excitons will dominate,resulting in red-shift luminescence.Moreover,effective and repeatable photocurrent responses can be found in these hybrids.     

A New 1D Iodoargentate Chain Based on Heptameric Ag_7I_(13) Building Units Templated by Transition-metalcomplex Cation: Structure,Fluorescence and Visible Light Responding Photocatalytic Property

Using transition-metal-complex cation as the structure-directing agent, a novel one-dimensional(1D) iodoargentate-based hybrid, namely, {[Co(2,2'-bipy)_3]_2(Ag_7I_(11))·3H_2O}_n(1) has been synthesized and structurally characterized. The interesting 1D(Ag_7I_(11))_n~(4n-) chain of 1 is constructed from a heptameric Ag_7I_(13) secondary building unit, in which abundant argentophilic interactions can be observed. Intermolecular C–H···π among [Co(2,2'-bipy)_3]~(2+) cations and C–H···I interactions between [Co(2,2'-bipy)_3]~(2+) cations and(Ag_7I_(11))_n~(4n-) chains contribute to the formation of a 3D network. The optical gap(2.58 eV) based on UV-Vis diffuse-reflectance measurement suggests the semiconductor nature of 1, which implies an efficient photocatalytic degradation activity on organic pollutants under visible light irradiation. As expected, 1 exhibits photocatalytic activity for the degradation of rhodamine B. The luminescence property was also studied.     

Enantiomeric Resolution on L—Carnitine Selective Polymers Prepared by Molecular Imprinting

L-carnitine selective polymers were prepared by molecular imprinting using methacrylic acid as the functional monomer. The acid function of the monomer is expected to form hydrogen bond and ionic interactions with the amine function of the target molecule L-carnitine.The imprinted polymers were used as stationary phases in high-performance liquid chromatography (HPLC). It was shown that L-carnitine imprinted polymer exhibited a higher affinity to its template molecule,while the non-imprinted polymer had no affinity to the compounds tested. Racemic carnitine hydrochloride was efficiently resolved on the L-carnitine imprinted polymer, and the separation factor is 1.9.     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

High pressure,a protocol to identify the weak dihydrogen bonds:experimental evidence of C–H···H–B interaction

Pressure, as a thermodynamic parameter, provides an appropriate method to detect weak intermolecular interactions. The C–H···H–B dihydrogen bond is so weak that the experimental evidence of this interaction is still limited. A combination of in situ high pressure Raman spectra and angle-dispersive X-ray diffraction(ADXRD) experiments was utilized to explore the dihydrogen bonds in dimethylamine borane(DMAB). Both Raman and ADXRD measurements suggested that the crystal structure of DMAB is stable in the pressure region from 1 atm(1 atm=1.01325×10~5 Pa) to 0.54 GPa. The red shift of CH stretching and CH_3 distortion modes gave strong evidence for the existence of C–H···H–B dihydrogen bonds. Further analysis of Raman spectra and Hirshfeld surface confirmed our proposal. This work provided a deeper understanding of dihydrogen bonds.And we wish that high pressure could be applied to identify other unconfirmed hydrogen or dihydrogen bond.     

The open-close mechanism of M2 channel protein in influenza A virus:A computational study on the hydrogen bonds and cation-π interactions among His37 and Trp41

The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interactions between His37 and Trp41. In the present study,the hydrogen bonding network of 4-methyl-imidazoles was built to mimic the hydrogen bonds between His37 residues,and the cation-π interactions between 4-methyl-imidazolium and indole systems were selected to represent the interac-tions between His37 and Trp41. Then,quantum chemistry calculations at the MP2/6-311G level were carried out to explore the properties of the hydrogen bonds and the cation-π interactions. The calcula-tion results indicate that the binding strength of the N-H···N hydrogen bond between imidazole rings is up to -6.22 kcal·mol-1,and the binding strength of the strongest cation-π interaction is up to -18.8 kcal·mol-1(T-shaped interaction) or -12.3 kcal·mol-1(parallel stacking interaction). Thus,the calcu-lated binding energies indicate that it is possible to control the permeation of the M2 ion channel through the hydrogen bond network and the cation-π interactions by altering the pH values.     

Structures,Properties and Theoretical Studies on Two Viologen/Iodoargentate Supramolecular Hybrids

Two iodoargentate hybrids templated by viologen or viologen-like cations, i.e. [MV(Ag_2I_4)]n(1) and [MBYP(AgI 2)]n(2),(MV~(2+) = methyl viologen, MBYP+ = 1-methyl-2,2?-bipyridine) have been synthesized in polar organic solvents.(Ag_2I_4)2-n and(Ag I2)2- n chains in both compounds were constructed from edge-sharing of normal and distorted Ag I4 tetrahedra, and a 2-D supramolecular layer based on C–H···I hydrogen bond was observed in 1. The band gaps of 1.54 and 2.67 e V indicated their semiconductor nature. Their band gap difference was led by different hydrogen bond donors in MV~(2+) and MBYP+, which result in more diffused p-π* antibonding orbitals in MV~(2+).     

Synthesis,Crystal Structure and Luminescent Property of a New Copper(Ⅰ) Iodide Complex Based on 3,5-Dimethyl-4-amino-triazole

The title compound,[Cu4I4(C4H8N4)4],has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group Pbca,with a=18.1851(10),b=9.3697(5),c=19.8034(10),V=3374.3(3)3,C16H32Cu4I4N16,Mr=1210.34,Z=4,Dc=2.383 g/cm3,μ=6.183 mm-1,F(000)=2272,S=1.032,the final R=0.0309 and wR=0.1180 for 3854 observer reflections(I2σ(I)).The structure of the title compound consists of tetranuclear copper cluster units bridged by the halogen atoms with the 3,5-dimethyl-4-aminotriazole ligands coordinated to the metal ions through the triazole nitrogen atoms.The luminescent property of 1 was also studied.     

Syntheses of Benzoxepinoquinolinone and Benzothiepinoquinolinone

l-Benzoxepino(3, 4-b)quinolin-l3(6H)-one and its halogen,alkyl, alkoxy derivatives Va'-d' and 1-benzothiepino(3,4-b}-quinolin- 13 ( 6H)-one Vf, and its alkyl derivatives Vg, weresynthesized through cyclization of 2-(substituted phenoxymethyl)-3-quinolinecarboxylic acids Va-d and 2-[ (un)substituted phen-ylthiomethyll-3-quinolinecarboxylic acids IVf-g in the presence ofpolyphosphoric acid.The acids IV were obtained from the corresponding ethyl-esters @ whcih were prepared through refluxing ethyl 2-bromo-methyl-3-quinolinecarboxylate(1) with substituted phenol or (un)substituted thiophenol in the presence of NaOEt.The compound Vg, was allowed to react with NBS, KaBH4, NH2OH-HCl to give compounds VII , VIII, and IX, respectively.The structures of 24 new compounds have been confirmed by elemental analysis, IR and 1H NMR.     

Synthesis,structure and magnetism of a novel Cu4^ⅡTi5^Ⅳ heterometallic cluster

A nonanuclear Cu4^ⅡTi5^Ⅳheterometallic cluster,[Ti5 Cu4 O6(ba)(16)](1,Hba=benzoic acid)was synthesized in one-pot reaction under the solvothermal condition.The metallic skeleton 1 contains a Ti5 core constructed from two vertex-shared Ti3 triangles and four separated Cu atoms outside which are connected together byμ3-O^2- ions.Total 16 ba ligands adoptμ2-η^1:η^1 coordination mode to protect the overall hetero metallic co re.Due to the unique d-d transitions of Cu^Ⅱion,the reflectance spectrum of 1 displays broad and strong absorption towards visible light extending to the near-infrared region.Moreover,1 shows almost purely paramagnetic behavior with the presence of weak antiferromagnetic interactions at low temperatures.     

Crystal Structure and Photoluminescence of a New Cadmium Complex with 6,7-Dicyanodipyridoquinoxalin

The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline (DICNQ) by solvothermal reaction gives rise to a coordination polymer [CdCl2(DICNQ)]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1: a = 6.756(1), b = 35.371(6), c = 7.027(1) , V = 1679.1(5) 3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm3, μ = 1.630 mm-1, F(000) = 904, S = 1.005 and T = 293(2) K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I > 2σ(I), and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states (DOS) calculations.     

Synthesis,structure and magnetism of a novel Cu_4~ⅡTi_5~Ⅳ heterometallic cluster

A nonanuclear Cu_4~ⅡTi_5~Ⅳ heterometallic cluster,[Ti_5 Cu_4 O_6(ba)_(16)](1,Hba=benzoic acid) was synthesized in one-pot reaction under the solvothermal condition.The metallic skeleton 1 contains a Ti_5 core constructed from two vertex-shared Ti_3 triangles and four separated Cu atoms outside which are connected together by μ_3-O~2 ions.Total 16 ba ligands adopt μ_2-η~1:η~1 coordination mode to protect the overall hetero metallic co re.Due to the unique d-d transitions of Cu~Ⅱ ion,the reflectance spectrum of 1 displays broad and strong absorption towards visible light extending to the near-infrared region.Moreover,1 shows almost purely paramagnetic behavior with the presence of weak antiferromagnetic interactions at low temperatures.     

Iodoplumbate(Ⅱ)-based Hybrid Templated by 1,4-Diazabicyclo[2.2.2]octane Derivative:Structure,Photocurrent Response Behavior and Photocatalytic Activity for the Degradation of Organic Dye

A new iodoplumbate/organic hybrid,[(Et_2DABCO)_2(Pb_3I_(11))(H3 O)]n(1,Et_2DABCO = N,N?-diethyl-1,4-diazabicyclo[2.2.2] octane) has been synthesized using solution method.According to X-ray diffraction structural analysis,the unique(Pb_3I_(11))_n~(5n-) chain in 1 is constructed from face-and edge-sharing PbI_6 octahedra,which is templated by(Et_2DABCO)~(2+) dication possessing both rigidity and flexibility.C–H···I hydrogen bonds contribute to the structure extending from 1D chains to a 3D network.Its energy band gap of 2.64 eV indicates its broad-gap semiconductor nature.It exhibits both photocurrent response property and photocatalytic activity for the degradation of rhodamine B.     

Synthetic Assembly of Inorganic-organic Polyoxometalate Hybrid Structures Employing Noncovalent Interactions between 5,6-Substituted 1,10-Phenanthroline Derivative Ligands

A new strategy for the synthesis of polyoxometalate-based(POM-based) metalorganic materials was developed. The approach takes the advantage of the ability of phenanthroline derivative base to build strong noncovalent interactions. Three POM-based metal-organic compounds, [Mn(MOPIP)_2(OH)_2][Mn(MOPIP)_2(OH)(SiW _(12)O_(40))]·6H_2O(1), [Cu_2(MOPIP)_2(OH)2(H_2O)]2-(Si W_(12)O_(40))·5H_2O(2) and [Co(Mo2O7)(MOPIP)]n(3)(MOPIP = 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), were synthesized under hydrothermal conditions. Single-crystal X-ray analysis reveals that compound 1 displays a mononuclear cluster. These clusters are interconnected by a framework of π···π stacking interactions to from a chain and layer structure. Compound 2 shows a multinuclear cluster with Keggin-type polyoxoanions [Si W_(12)O_(40)]4- as building blocks. Strong hydrogen bonding interactions extend these multinuclear clusters into a two-dimensional layer. Compound 3 is a coordination polymer, in which [Mo_2O_7]2- polyoxoanions connect the Co(Ⅱ) ions running along the direction of one of the crystallographic axes to from a linear chain. Adjacent chains are further assembled into a two-dimensional network by strong hydrogen bonding interactions. The main structural traits in all of the compounds are that polyoxometalate acts as inorganic building blocks and connect metal ions to form cluster structure and coordination polymer. In addition, the photocatalytic activities and mechanism of compounds 1~3 on the degradation of Rhodamine B(Rh B) under UV irradiation have been investigated in detail.     

UV LASER INITIATED STEREOSELECTIVE HOMOGENEOUS CATALYSIS POLYMERIZATION OF PHENYLACETYLENE

In this paper, the stereoselective homogeneous catalysis polymerization of phenylacetylene by using two kinds of catalysts W(CO)_5CH_3I and W(CO)_4I_2 produced from UV laser photolysis of W (CO)_6 in CH_3I, I_2—C_6H_6 and CHI_3—C_6H_6 respectively was studied. The effects of laser energy, laser irradiation time and lifetime of catalyst on the polymerization of phenylacetylene were discussed. The photoproducts of W (CO)_6 in CH_3I, I2—C_6H_6 and CHI_3—C_6I_6 were determined by IR spectra. The structures of polyphenylacetylene obtained by W (CO)_5CH_3I and W (CO)_4I_2 catalysts were characterized by IR spectra and ~1H NMR spectra.     

ANALYSIS OF FRAGMENT INTERACTION AND ASSIGNMENT OF ELECTRONIC SPECTRUM FOR COMPLEX ION[S2MoS2FeCl2]^2—

<正> The electronic structures of complex ion [S2MoS2FeCl2]2- (1) and its fragments MoS42- (2) and FcCl2(3) have been calculated base on the LCAO-HFS method with restricted open shell or closed shell. The interaction between the fragments 3 and 2 and the formation of complex ion 1 have been discussed. It was found that the Fe(Ⅱ) donated electrons to the Mo(Ⅵ)and accepted electrons from the sulphur ligand and that the stability of complex ion 1 is contributed from both direct and indirect interactions through the bridging sulphur atoms. In addtion, the electron transition energies of complex ion 1 were calculated and its electronic absorptions were assigned. It was shown that the calculated wavelengths of the absorption bands are in agreement with the observed ones.