Crystal Structure of a Novel Supramolecule Made Up of Bis(μ_2-aqua)aqua(3-carboxy acrylate) monosodium(Ⅰ)

The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.

Comparative Study on the Inclusion Complexation of Rutin with Cyclodextrin Supramolecules

The interaction of beta-cyclodextrin(beta-CD), hydroxypropyl-beta-CD and gamma-CD with the drug rutin has been investigated by using fluorimetry. The stoichiometry of the complexes and their formation constants have been estimated. The thermodynamic parameters for the formation of complexes were obtained. The complexing ability of HP-beta-CD is remarkably stronger than beta-CD and gamma-CD.

Folic acid-based supramolecules for enhanced stability in potassium ion batteries

Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries(PIBs)because of their abundant,recyclable and highly customizable characteristics.However,small molecular organics are easily solubilized in organic electrolytes,resulting in a low capacity and poor stability.Herein,the folic acid-based supermolecules(SM-FAs)are successfully prepared by a hydrothermal assisted self-assembly strategy.Due to multi-locus hydrogen bonds(HBs)and the cyclizedπ-conjugated interactions,the structural stability of SM-FAs has been significantly improved,and the solubility in carbonate electrolytes has been effectively inhibited.As an anode for PIB,the SM-FA-6sample exhibits a large capacity(206 mAh/g at 50 mA/g)and an outstanding cycle stability(capacity retention of 91%after 1000 cycles at 50 m A/g).More impressively,an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K^(+),and the atypicalπ–K^(+)interaction within the assembled conjugation framework,is unraveled for potassium ion accumulation.It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.

Structural studies of dicycloplatin,an antitumor supramolecule

The solubility and stability of platinum-based anticancer agents have a direct bearing on their activity and toxicity.Much research has been conducted over the past decades in order to prepare drugs such as cisplatin and carboplatin with improved efficacy and reduced toxicity.Based on the premise that supramolecular platinum agents may have superior physicochemical properties,we successfully designed a novel anticancer agent,dicycloplatin,which has proven to be active against a number of human malignancies.The crystal structure of dicycloplatin has been determined.An aqueous solution of dicycloplatin was also studied using electrospray ionization mass spectrometry (ESI-MS).Based on the experimental observations,a model of the structure in aqueous solution is proposed which explains both the higher solubility and higher stability of dicycloplatin compared with carboplatin.

Synthesis of mid-dicarboxy polystyrene by ATRP and formation of ionic-bonded supramolecules

Dimethyl 4,6-bis(bromomethyl)isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styrene successfully.Results showed that the process had some of the good characteristics of controlled/living free radical poly-merization.The molecular weight of the obtained polymer increased linearly with monomer conversion,its molecular weight distribution was very narrow,and a linear relationship between ln([M]0/[M])and polymerization time was found.A well-defined novel structural polystyrene containing two ester groups in the mid-main chain was prepared with con-trolled molecular weight and narrow polydispersity.The structure of the polymer was confirmed by 1H-NMR spectra.After being hydrolyzed,dicarboxy polystyrene was obtained and used to form ionic-bonded supramolecules with 1-dodecanamine as a model of the star-shaped supramolecules.The supramolecules formed were characterized by Fourier transform infrared(FTIR)spectrum.

Ionothermal Synthesis and Characterization of Two Polyoxometalate-based Supramolecules

Two novel 3D supramolecular architectures with hexamolybdate and phosphotungstate anions were syn- thesized under ionothermal conditions. The structures were named as [Cut（L1）2]2L2[Mo6O19]（1） and [Cur（L3）2]2.5· H0.5[PW12O40].H2O（2）（L1=2,2＇-bipyridine, L2=4,4＇-bipyridine, L3=2,2＇-biimidazole） and characterized via Fourier transform infrared spectroscopy（FTIR） and FT-Raman spectroscopy analyses. Single-crystal X-ray diffraction analysis revealed that the two compounds crystallized in the space group P1 and were constructed through hydrogen bonding.

Carbonate-Water Supramolecule Trapped in Silver Nanoclusters Encapsulating Unprecedented Ag_(11) Kernel

In the absence of inorganic anion templates and in high pH condition(pH∼14),an unprecedented carbonate-hydrate supramolecule,[(CO_(3))_(2)(H_(2)O)]^(4−),trapped from atmospheric CO_(2),found to play an anion templating role to support the architecture of two related silver(Ag)nanoclusters(SD/Ag54a and SD/Ag55a),which are coprotected by the same organic ligands but differ by one silver atom of the metallic frameworks.Two[(CO_(3))_(2)(H_(2)O)]^(4−)supramolecules are trapped into two Ag/tBuPhS/dppm pods,connected by a pair of face-shared silver pentagonal bipyramids(Ag_(11))into peanut-shaped silver nanoclusters.Interestingly,the equatorial Ag_(11) kernel represents a new embryonic ultrasmall silver nanocluster that is thought to follow a special facesharing growth fashion from pentagonal bipyramidal Ag7 subunit,which is also structurally elucidated in another new Ag44 nanocluster(SD/Ag44c)obtained in similar assembly system just changing tBuPhS−to iPrPhS−ligand.The isolation of SD/Ag54a and SD/Ag55a were associated with:(1)supramolecule induction and(2)reductive and carbonate-rich assembly system.First,this work brings a fresh perspective on the role of carbonate-water anion supramolecule in directing the assembly of silver nanoclusters.Second,it realizes the control of reduction kinetics and kernel growth using multiple weak reductants and thiolate ligands.Third,it provides a possible face-shared growth route for ultrasmall silver nanoclusters.

Defect Engineering of Disordered Carbon Anodes with Ultra-High Heteroatom Doping Through a Supermolecule-Mediated Strategy for Potassium-Ion Hybrid Capacitors

Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons could enhance their reversible capacities.Nevertheless,most lignocellulose biomasses lack heteroatoms,making it a challenge to design highly heteroatom-doped carbons(>10 at%).Herein,we report a new preparation strategy for amorphous carbon anodes.Nitrogen/sulfur co-doped lignin-derived porous carbons(NSLPC)with ultra-high nitrogen doping levels(21.6 at%of N and 0.8 at%of S)from renewable lignin biomacromolecule precursors were prepared through a supramolecule-mediated pyrolysis strategy.This supermolecule/lignin composite decomposes forming a covalently bonded graphitic carbon/amorphous carbon intermediate product,which induces the formation of high heteroatom doping in the obtained NSLPC.This unique pyrolysis chemistry and high heteroatom doping of NSLPC enable abundant defective active sites for the adsorption of K+and improved kinetics.The NSLPC anode delivered a high reversible capacity of 419 mAh g^(-1)and superior cycling stability(capacity retention of 96.6%at 1 A g^(-1)for 1000 cycles).Potassiumion hybrid capacitors assembled by NSLPC anode exhibited excellent cycling stability(91%capacity retention for 2000 cycles)and a high energy density of 71 Wh kg^(-1)at a power density of 92 W kg^(-1).

Hydrothermal Synthesis and Characterization of a Novel Supramolecular Network Compound [Co(IN)_2(H_2O)_4](IN=Isonicotinate)

A novel supramolecular compound, [Co(IN)_2(H_2O)_4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Though the unit cell structure of the title compound is only monomeric, all these units as building blocks are assembled into a novel three-dimensional supramolecular network via the widely hydrogen-bonding and π-π stacking interactions.

Synthesis and crystal structures of La(Ⅲ),Y(Ⅲ) complexes of homoveratric acid with 1,10-phenanthroline

Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emission spectra.The crystal structures were determined with single crystal X-ray diffraction method.The two compounds were isostructural,and 3D supramolecule architectures were formed by hydrogen bonds and π-π stacking interactions.They strongly emitted upon excitation due to π→π transition of th...

Synthesis and Crystal Structure of a Two-dimensional Framework Supramolecular Complex [Mn(phen)(DPZDA)(H_2O)]·2H_2O

A novel two-dimensional supramolecular complex [Mn（phen）（DPZDA）（H2O）]·2H2O has been synthesized by the reaction of Mn（CH3COO）2, 1,10-phenanthroline （phen） and H2DPZDA （3,5-dimethyl-pyrazine-2,6-dicarboxylic acid）. Elemental analysis, IR spectra and X-ray singlecrystal diffraction were carried out to determine the composition and crystal structure of the title complex. Crystal data： triclinic system, space group P1, a = 7.7474（13）, b = 9.3381（15）, c = 15.146（3） A, α = 93.872（3）, β= 102.451 （11 ）, y = 105.261 （ 11）°, C20H20MnN4O7, Mr = 483.34, Z = 2, F（000） = 498, V=1023.2（3）A^3, Dc=1.569 g/cm^3,μ=0.697 mm^-1, -9≤h≤9, -11≤k≤10, -18≤l≤12, R = 0.0365 and wR=0.0901 for 3585 independent reflections （Rint= 0.0165） and 2923 observed reflections （I〉 2σ（I））. Structural analysis indicates that Mn（Ⅱ） adopts a distorted octahedral geometry. The 2-D framework supramolecular structure of the title complex is constructed from hydrogen bonds and π…π interactions.

Synthesis and Crystal Structure of the Binuclear Complex:[Cu_2(phen)_2(ip)(Hip)_2]·4H_2O

A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex： monoclinic, space group C2/c, a = 19.214（3）, b = 10.6973（14）, c = 22.567（3） A, β = 105.081（2）°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F（000） = 2160, V= 4478.6（10） A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 （Rint = 1.0357） independent reflections and 3290 observed ones （I 〉 2σ（I））. Structural analysis shows that coordination geometry of Cu（ Ⅱ ） is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.

Molecular Dynamic Simulation for HMX/NTO Supramolecular Explosive

Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramolecular explosive was investigated by the molecular dynamic (MD) method. Interaction between oxygen atoms in HMX and hydrogen atoms in NTO or between hydrogen atoms in HMX and oxygen atoms in NTO were studied by the radial distribution function (RDF). It shows that there are strong hydrogen bonds and Van Der Waals forces between HMX and NTO, in which the hydrogen bonds between oxygen atoms in the NTO and hydrogen atoms in HMX are the main host-guest interactions. The distributions of bond length, bond angle and dihedral angle were simulated by MD. It shows that the structure of HMX is seriously distorted. The binding energies and X-ray powder diffraction (XRD) patterns were calculated on the basis of the final HMX/NTO supramolecular structures. The results show that the binding energies of six supramolecular models are E binding (1 1 1-) >E binding (1 0 0)>E binding (0 2 0)>E binding (random)>E binding (1 0 2-)>Ebinding (0 1 1), and the XRD patterns of six supramolecular models are quite different from pure HMX or NTO. Based on the investigation for growth morphology, binding energies and RDF, the model of HMX supercell substituted by NTO along the (1 1 1-) surface of HMX is easier to form.

Layered Lanthanum Complex with 3-Nitrophthalic Acid Assembled via Hydrogen Bonds-Synthesis, Structure and Characterization of [LaL(HL)(H_2O)_3]_2·2H_2O (H_2L=3-NO_2C_6H_3(CO_2H)_2)

A new dinuclear centrosymmetric complex [LaL（HL）（H2O）3]2（2H2O （H2L = 3-nitrophthalic acid, NPA） was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The complex crystallizes in triclinic system, space group P1^- with a = 8.1549（16）, b = 8.8856（18）, c = 15.277（3）A,α= 100.93（3）,α= 90.81（3）, γ= 104.56（3）°, V = 1049.8（4）A^3, Z = 1,μ= 2.125 mm^-1, Dc=1.994 g/cm^3, R = 0.0259 and wR = 0.0679. Two 3-nitrophthalates（2-） coordinate with the La3＋ ions in a bridging mode, and two monohydrogen- 3-nitrophthates（1-） and three waters in terminal ways, respectively. Each La^3＋ ion is nine-coordinated to exhibit a distorted tricapped trigonal prism coordination polyhedron. Both the coordinated and crystal waters are involved in the inter- and intramolecular hydrogen bonds. The dinuclear units are linked into a 2D network structure in the ab plane via intermolecular hydrogen bonds along the axes a and b. Two crystal waters fill each rhombic pore of the network. The networks are further packed along the c axis forming a layered supramolecular structure through the C-H…O weak forces between the adjacent sheets. TGA analysis shows the complex undergoes the loss of waters of crystallization and coordination and the decomposition of ligands sequentially.

Synthesis and Crystal Structure of Co(DMSO)_2(H_2O)_2(SCN)_2 with One-dimensional Hydrogen-bonded Structure (DMSO = Dimethylsulfoxide)

The title complex Co（DMSO）2（H2O）2（SCN）2 has been prepared and structurally characterized. It crystallizes in monoclinic, space group P21/n with a= 5.1981（9）, b = 11.944（2）, c = 12.646（2） A,β = 98.686（2）°, V = 776.2（2） A^3, C6H16CoN2O4S4, Mr = 367.38, Z = 2, De = 1.572 g/cm^3, F（000） = 378 and μ（MoKa） = 1.646 mm^-1. The structure was refined to R= 0.0232 and wR = 0.0645 for 1241 observed reflections with I 〉 2σ（I）. In the title complex, each Co（II） atom is octahedrally coordinated by four O atoms from two DMSO ligands and two water molecules as well as two N atoms from SCN^- ions. The title molecules are connected to each other through intermolecular hydrogen bonds to form a 1-D structure extended by eight-membered Co2O4H2 rings.

Lanthanide Complex [Nd(dpdo)_4(H_2O)_3][ClO_4]_3·4.5H_2O·dpdo Containing Framework Based on 4,4′-Dipyradine-Dioxide

A novel lanthanide coordination polymer formulated as [Nd(dpdo) 4(H 2O) 3] 3·4.5H 2O·dpdo 1(dpdo=4,4′-dipyrazine-dioxide) was synthesized and structurally characterized. The Nd 3+ ions are bridged by dpdo ligands in a cis-mode to form a zigzag chain along direction. Meanwhile, each Nd 3+ ion is coordinated with three terminal dpdo molecules. One of them is overlapped with the bridging one through π-π stackings, and the other two are bound to the opposite directions of the bridging ones, producing a ribbon-like motif with rectangular cavity. These adjacent ribbons are connected through inter-molecular π-π stackings to give parquet-like architecture with a large rectangular channel (1.108 nm×1.660 nm) in which the crystal lattice water molecules and ClO 4 - anions are included. Thermal analysis shows that the solvate dpdo and water molecules can be removed at lower temperature, while coordinated dpdo molecules are lost simultaneously at higher temperature.

Photoinduced Electron Transfer in Host-Guest Complexes of Naphthalene Derivatives with p-NBCD and m-NBCD

A number of naphthalene derivatives containing adamantanamine binding moiety and an （CH2）. （n = 2, 3, 4, 5, 6） spacer were prepared as electron donor. A supramolecular assembly was fabricated by the inclusion complexation of the donor substrates with the host molecules, mono-6-O-p-nitrobenzoyl-β-cyclodextrin （p-NBCD） and mono-6-O-m-nitrobenzoyl-β-cyclodextrin （m-NBCD）, in water. The fluorescence quenching in these systems was studied and detailed Stern-Volmer constants were measured. It revealed that an efficient photoinduced electron transfers （PET） between the naphthalene donors and the cyclodextrin acceptors occurred.

Hydrothermal synthesis of 3D porous architectures

A novel porous lanthanide-organic coordination polymer, [Nd（H2O）（HnicO）（TP）]·2H2O （1） （H2nicO=2-hydroxynicotinic acid, TP= terephthalate）, was prepared under hydrothermal condition and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound 1 exhibited a flexible coordination geometry of lanthanide ions, which possessed a three-dimensional （3D） open framework with one-dimensional （1D） channels containing lattice water molecules. This framework structure exhibited a high stability up to 330℃ after removing free water molecules. A homometallic supramolecular framework （Zn（HnicO）2（H2O）2 （2）） was obtained due to the competitive reaction between organic ligands, Nd3＋ and Zn2＋ ions. The results showed that on the basis of the soft-hard/acid-base principle the coordination selection between metal ions and organic ligands played an essential role in the smart construction of lanthanide architectures.

Synthesis and Crystal Structure of 2-Fluoro-4-methyl-3-oxo-4-aza-5α-androst-1-ene-17β-carboxylic Acid Methyl Ester

The title compound VII, 2-fluoro-4-methyl-3-oxo-4-aza-5α-androst-1-ene-17β-carboxylic acid methyl ester （C21H30FNO3, Mr = 363.46）, was prepared through a seven-step reaction from pregnenolone, and characterized by elemental and single-crystal X-ray diffraction analyses as well as IR, MS and 1H-NMR spectra. It is of monoclinic system, space group P21/c with a = 6.3882（7）, b = 9.9033（11）, c = 15.4925（17） , β = 91.923（2）°, V = 979.57（19） 3, Z = 2, Dc = 1.232 mg/m3, μ = 0.088 mm-1, F（000）= 392, R = 0.0465, wR = 0.0989 and λ（MoKα） = 0.71073 . The structure indicates that the four cycles （A： C（1）–C（2）–C（3）–N（1）–C（5）–C（10）, B： C（5）–C（6）–C（7）– C（8）–C（9）–C（10）, C： C（8）–C（14）–C（13）–C（12）–C（11）–C（9）, D： C（14）–C（15）–C（16）–C（17）–C（13）） are in chairand trans-configurations. The results of crystal structure determination show that there exist weak intra-molecular hydrogen bonds, resulting in a two-dimensional supramolecular frame-work of the title compound.