Synthesis,Crystal Structure and Water Vapor Adsorption Property of a New Supramolecular Architecture

A new complex, [Cu（HL）（phen）（H2O）]·4H2O（1, H3L·HCl = 5-（（4-carboxypiperidin-1-yl）methyl）isophthalic acid hydrochloride, phen = 1,10-phenanthroline）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.5520（14）, b = 12.6659（12）, c = 15.5006（14） A, β = 97.224（2）o, V = 2834.3（5） A3, Z = 4, C27H33N3O11 Cu, Mr = 639.10, Dc = 1.498 g/cm3, μ = 0.837 mm-1, S = 1.047, F（000） = 1332, the final R = 0.0423 and w R = 0.1118 for 18772 observed reflections（I 〉 2σ（I））. The compound is a Cu（Ⅱ） centre mononuclear molecule in the asymmetric unit. The independent binuclear [Cu2（HL）2（phen）2] units are bridged to form a three-dimensional（3D） supramolecular polymer by extensive hydrogen bonds and π-π non-covalent bonding interactions. Moreover, thermogravimetric（TG） analysis and gas adsorption property of 1 were also discussed.

A Novel Borophosphate Coordination Polymer with Sandwich-type Supramolecular Architecture

A novel borophosphate (Hmel)3{Co2[(mel)2(HPO4)2(PO4)]·H3BO3·H2O} (mel= melamine) has been synthesized under mild solvothermal conditions. The structure of the compound exists a high ordered organic-inorganic sandwich-type supramolecular architecture via metal-coordination, hydrogen bonds and π-π stacking interactions.

Effects of Doubled_CO_2 Concentration on Ultrastructure, Supramolecular Architecture and Spectral Characteristics of Chloroplasts from Wheat

Wheat ( Triticum aestivum L.) plants were grown under ambient and doubled_CO 2(plus 350 μL/L) concentration in cylindrical open_top chamber to examine their effects on the ultrastructure, supramolecular architecture, absorption spectrum and low temperature (77 K) fluorescence emission spectrum of the chloroplasts from wheat leaves. The results were briefly summarized as follows: (1) The wheat leaves possessed normally developed chloroplasts with intact grana and stroma thylakoid membranes; The grana intertwined with stroma thylakoid membranes and increased slightly in stacking degree and the width of granum, in spite of more accumulated starch grains within the chloroplasts than those in control; (2) The particle density in the stacked region of the endoplasmic fracture face (EFs) and protoplasmic fracture face (PFs) and in the unstacked region the endoplasmic fracture face (EFu) and the protoplasmic fracture face (PFu) was significantly higher than that of control. Furthermore, in some cases many more particles on EFs faces of thylakoid membranes appeared as a paracrystalline particle array; (3) The variations in the structure of chloroplasts were consistent with the absorption spectra and the low temperature (77 K) fluorescence emission spectra of the chloroplasts developed under the doubled_CO 2 concentration. Results indicate that the capability of light energy absorption of chloroplasts and regulative capability of excitation energy distribution between PSⅡ and PSⅠ were raised by doubled_CO 2 concentration. This is very favorable for final productivity of wheat.

Novel Hydrogen-bonded Three-dimensional Supramolecular Architectures Containing 2D Honeycomb Networks or 2D Grids

Two new supramolecular complexes, [Cu（H2dhbd）（3-pyOH）（H2O）]2·3-pyOH·2H2O （1） and [Cu2（dhbd）（dpa）2- （H2O）]·6H2O （2） （Hndhbd=2,3-dihydroxybutanedioic acid, 3-pyOH=3-hydroxypyridine, dpa=2,2＇-dipyridylamine）, have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses, UV-Vis and IR spectra, and TGA analysis. X-ray structural analysis revealed that, through four pairs of strong O…H-O hydrogen bonds, the cyclic dinuclear units in 1 together with four adjacent neighbors are connected into a 2D honeycomb network encapsulating free 3-pyOH ligands. Unexpectedly, the water-dimers are fixed in interlayers of 2D honeycomb network and act as hydrogen-bond bridging to further extend these 2D networks into 3D hydrogen-bonded framework. Complex 2 includes interesting 2D grids constructed from chiral dinuclear units through strong O…H-O and O…H-N hydrogen bonding, which are extended through other crystallization water molecules into three dimension with channels. Variable-temperature magnetic susceptibility measurements for both complexes indicate the presence of weak antiferromagnetic exchange interactions between adjacent copper（Ⅱ） ions.

Progress in the Supramolecular Architecture-directed Synthesis of Perfect Ladder Polysiloxanes

1 Introduction Ladder polysiloxanes (LPSs) including organo-bridged ladder polyorganosiloxanes (R-OLPSs, R is side group) and ladder polyorganosilsesquioxanes (R-LPSQs) have intrigued polymer chemists for about 50 years due to their excellent resistance to all kinds of degradations. However, their synthesis has been a great challenge to polymer chemists. Here, we describe a new approach based on supramolecular concerted interactions as follows.2 Results2.1 Synthesis of Perfect R-OLPSsA series of real ...

Two Zinc Architectures:A Mononuclear Complex and a 2D Wave-like Organic-inorganic Hybrid Layer

Self-assembly of Zn（NO3）2·6H2O and 2,3,5,6-tetrabromoterephthalic acid（H2TBTA） gave rise to two new zinc metal-organic frameworks,Zn（HTBTA）2（phen）2·H2O（1） and Zn（TBTA）1/2（μ2-OH）（H2O）·0.25EtOH（2）.Complex 1 is a mononuclear molecule.The hydrogen bonding interactions further connect the mononuclear molecules to generate a 2D supramolecular architecture.Complex 2 is a 2D organic-inorganic hybrid layer framework constructed from 1D rod-shaped secondary building units.

A Two-dimensional Supramolecular Complex Constructed by 1,10-Phenanthroline Derivative Ligand:Synthesis,Structure and Luminescence

An unusual two-dimensional supramolecular complex, namely, [Cd2（Cl）4（L）2]（1）, has been synthesized by 2-（1 H-imidazo[4,5-f][1,10]phenanthrolin-2-yl）phenol（L） and CdCl2·2.5H2O under hydrothermal conditions. The compound was characterized by elemental analysis, TG and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.151（2）, b = 14.119（3）, c = 14.744（3） ？, α = 115.744（4）, β = 108.063（4）, γ = 93.371（4）o, V = 1762.7（7） A°^3, Z = 2, C（38）H（24）Cd2Cl4N8O2, Mr = 991.25, Dc = 1.868 g/cm^3, F（000） = 976, μ（Mo Ka） = 1.560 mm^-1, R = 0.0639 and w R = 0.1307. In 1, two Cd（II） atoms are bridged by two chroline atoms to give a dimer. Neighboring dimers are linked by N–H···Cl hydrogen bonds to afford supramolecular chains, which are further joined together by π-π interactions to result in a supramolecular layer. In addition, luminescent property and thermal behavior of compound 1 have been studied.

Synthesis, Crystal Structure and Photocatalytic Properties of a Supramolecular Assembly Based on Keggin Polyoxotungstate

A new supramolecular compound （4,4＇-bipyH）4[SiW12O40]（4,4＇-bipy） （4,4＇-bipy = 4,4＇-bipyridine） was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767（12）, b = 21.1879（11）, c = 15.6942（8） A, β = 97.068（3）°, V = 7351.3（7） A3, Cs0H44N10040SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F（000） = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiWl2O40]4- anion, one 4,4＇-bipy and four protonated （4,4＇-bipyH）＋ cations. The [SiWl2O40]4- anion and protonated 4,4＇-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.

Syntheses and Crystal Structures of a Cadmium(Ⅱ) and a Zinc(Ⅱ) Complexes with the Flexible Ligand 1-Acetic Acid-2, 2'-biimidazole

Reactions of NaAcebiim （NaAcebiim = 1-acetic acid-2, 2＇-biimidazote monoso- dium salt） and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd（Acebiim）（NO3）（H20）]n （1） and 0D [Zn（Acebiim）2（H20）2]＇2H20 （2） in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group Pi, and 2 is of monoclinic system, space group P2 1/n. In 1, two nitrate groups link two Cd（Ⅱ） ions forming [Cd2（NO3）2（H20）2] as secondary building units that are interconnected by the Acebiim ligand into an infinite ladder. In2, the hydrogen-bonded synthon R22（16） between the N-H moieties and carboxylic acid link [Zn（Acebiim）2（H20）2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.

Synthesis, Crystal Structure and Thermal Stability of a New Cadmium(II) Polymer Based on 1H-pyrazole-3-carboxylic Acid Ligand

A novel Cd（Ⅱ） coordination polymer, [CdCI（Hpc）H2O]n （1, H2pc = 1H-pyrazole-3- carboxylic acid）, was synthesized by the reaction of CdCl2·2.5H2O with H2pc, and structurally characterized by IR spectrum, UV-Vis spectrum, elemental analysis, single-crystal X-ray diffraction, as well as thermal analysis. Compound 1 crystallizes in monoclinic, P21/n space group with α = 7.0304（3）, b = 10.3047（3）, c = 10.6446（4） A, β= 107.174（4）°, F = 736.78（5） A^3, Z = 4, C4HsCdClN2O3, Mr = 276.95, Dc = 2.497 g/cm%3, F（000） = 528.0,μ= 3.281 mm^-1, R = 0.0169 and wR = 0.0387. The central metals adopt distorted octahedral geometry. Carboxyl groups of the ligand connect Cd（Ⅱ） into a one-dimensional chain, which further constructs a two-dimensional network by halogen bridging. Such two-dimensional structures are finally connected into a three-dimensional supramolecular architecture due to the hydrogen bonds and intermolecular π…π interactions. In addition, complex 1 has high thermal stability.

Synthesis,Crystal Structure and Thermal Stability of Homopolytungstate Supporting Nickel(Ⅱ) Coordination Fragments

The orsano-inorganic hybrid compound [ Ni（phen）3] [ （H2W12O40） { Ni（phen）2H2O} { Ni（trien） } ]·2H2O was synthesized from Na2 WO4·2H2O, NiSO4·6H2O, CH3COOK, triethylenetetramine and 1,10-phenanthroline in water by the hydrothermal reaction, and characterized by IR, X-ray single crystal diffraction, and TG-DTA analysis. This compound crystallized in the monoclinic system, space group P2 （1）/n, with lattice constants： a =1.80998 （6） nm, b =2.36504（8） nm, c =2.29199（7） nm,β= 110.2220（10）°, V=9.2065（5） nm, Z=4. Final R indices R1=0.0532. ωR2=0.1295. The compound is decomposed at 593℃.

Two Coordination Polymers Based on the Flexible N-Substituted 2,2'-Biimidazole Ligand: Solvothermal Synthesis, Crystal Structures and Characterizations

Two new supramolecular complexes, [Cu2（Pra2biim）2（H2O）2].2H20 （1） and[Mn（Pra2biim）（H2O）E]n （2） （HEPraEbiim = 1,1′-di（propionic acid）-2,2′-biimidazole） have beenprepared and structurally characterized by thermogravimetric analysis, elemental analysis, IRspectra and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals thatcomplex 1 crystallizes in the triclinic, space group P1 with a = 8.403, b=9.60970（10）, c =10.5681（2） A, V= 736.272（16） A3, Z= 1, Dc = 1.695 g/cm^3, F（000） = 386, GOOF = 1.156, R（I〉20（/）） = 0.0396 and wR （I 〉 20（/）） = 0.1060, and exhibits a dinuclear structure formed by theconnection of Cu^2＋ ions with two bridging Pra2biim2 ligands. Complex 2 crystallizes in themonoclinic, space group Pc with a = 9.058（4）, b = 5.2745（16）, c = 17.591（7） A, V= 733.2（5） A3, Z= 2, Dc=1.663 g/cm^3, F（000） = 378, GOOF = 1.060, R（I〉 2σ（I）） = 0.0885 and wR（1 〉 2σ（I）） =0.2199, and the Pra2biim2 ligands link Mn^2＋ ions to a 63 2D sheet structure. The Pra2biim2′ ligandshows two different types of coordination modes. Moreover, hydrogen bonds further stabilize the3D supramolecular architecture. The magnetic behavior in the temperature range （2-300 K）reveals weaker antiferromagnetic interactions between the Cu2＋ ions in 1.

Syntheses and Structures of Two Complexes Based on Mixing Carboxylate Ligands and Imidazole-containing Ligands

Two novel complexes, [Zn（L2-1）（L2）]（1） and [Ni（L2-3）（L4）·2H2O]（2）, have been synthesized by solvothermal reactions in different solvents through mixing the carboxylate ligand, imidazole-containing ligand and the metal salt. Compound 1 crystallizes in monoclinic, space group P21/c with a = 9.21400（15）, b = 18.1172（3）, c = 15.7669（2） A, β = 91.1769（13）o, C30H26N4O4 Zn, Mr = 571.92, V = 2631.44（7） A3, Z = 4, Dc = 1.444 g·cm-3, μ = 1.659 mm-1, F（000） = 1184, λ（Cu Kα） = 1.54178 A, the final R = 0.048, w R = 0.1442 and S = 1.139. Compound 2 crystallizes in triclinic, space group P1 with a = 7.0664（3）, b = 9.5265（4）, c = 12.8861（6） A, α = 74.066（4）, β = 87.408（3）, γ = 83.591（3）o, C34H32N6O6S2 Ni, Mr = 743.49, V = 828.83（6） A3, Z = 1, Dc = 1.490 g·cm-3, μ = 2.490 mm-1, F（000） = 386, λ（CuK α） = 1.54178 A, the final R = 0.0315, w R = 0.0861 and S = 1.022. Complex 1 is the 1D chain which is linked by C–H···O hydrogen bonding interactions to form a 2D supramolecular architecture. Meanwhile, complex 2 is a 2D（4,4） network with the ABCABC stacking mode and then generates a 3D supramolecular architecture through C–H···N and O–H···O hydrogen bonding interactions.

A Cobalt Supramolecular Compound Constructed from 4,6-Di（1-imidazolyl）- 1,3,5-triazine-2-one： Synthesis, Characterization and Magnetic Property

A cobalt（II） coordination polymer, [Co（dimto）2（H2O）2]·4H2O[1, dimto=4,6-di（1-imidazolyl）-1,3,5- triazine-2-one], has been prepared under solvothermal condition. Single-crystal structural analysis reveals that compound 1 crystallizes in the orthorhombic space group Ibca（No.73） with a=1.80696（12） nm, b=1.93224（11） nm, c=1.36798（10） nm, V=4.7763（5） nm3 and R1=0.0438. Compound 1 is a 3D supramolecular architecture composed of 1D wave-like chains with hydrogen bonds and π-π interactions. Compound 1 was further characterized by powder X-ray diffraction（PXRD）, infrared（IR） spectroscopy, thermogravimertic analysis（TG） and elemental analysis. Additionally, the magnetic property of compound 1 was also investigated.

A General Approach for Synthesis of Circularly Assembled Supramolecular Polymers by Means of Region-confined Amphiphilic Supramolecular Polymerization

Topological supramolecular polymers are responsible for design of innovative materials with unique physical properties but remain a challenging task to prepare by means of supramolecular polymerization.In this contribution,we present a novel method of region-confined amphiphilic supramolecular polymerization(RASP)in a controllable two-step self-organization pathway,which was certified by a new type of pyridine-oxadiazole alternating 48-membered macrocycles with structurally regional distribution of distinct self-assembling groups that can self-organize into circular supramolecular architectures.Meanwhile,water molecule plays a crucial role in RASP,and the water content in nonpolar solvent chloroform is sensitive to trigger controllable amphiphilic self-organization.Moreover,differing from the traditional rodlike micelles formed by self-assembly of linearly amphiphilic molecules,this approach of RASP exclusively gives rise to the formation of circularly assembled supramolecular polymers.

Macrocyclic-ligand Induced Synthesis of Aryl Ethynides with Divergent Silver（I） Clusters

Two structurally characterized metal-cluster-centered supramolecular architectures named [Ag8（1,2-（C= C）2-C6H4）（Py[6]）（CF3CO2）6]·2.5MeOH （1） and [Ag12（1,2,4,5-（C=C）aC6H2）（Py[6]）2（CF3SO3）s]·4MeOH·3H2O （2） are synthesized through the interaction with a bowl-shaped macrocyclic ligand PyI61. Particularly, two dissimilar silver（I） clusters are resulted in 2 within the structure under the influence of the macrocyclic ligand Py[6]. Such dissimilarity of the silver（1） cluster is also reflected on the structural and photophysical differences between 1 and 2.