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91.
Mit"kina T. V. Gerasko O. A. Sokolov M. N. Naumov D. Yu. Fedin V. P. 《Russian Chemical Bulletin》2004,53(1):80-85
Slow evaporation of hydrochloric acid solutions of zirconium(iv) or hafnium(iv) oxochlorides and cucurbituril in air afforded compounds with composition [M4(OH)8(H2O)16]Cl8·(C36H36N24O12)·16H2O, where M = Zr (1) or Hf (2). According to the X-ray diffraction data, complexes 1 and 2 are isostructural. Their crystal structures can be described as packings of polymer chains consisting of alternating cucurbituril molecules and tetranuclear cations [M4(OH)8(H2O)16]8+ linked to each other via an extensive network of hydrogen bonds. Compound 2 is the first structurally characterized tetranuclear hafnium aqua complex. 相似文献
92.
Moncada MC Parola AJ Lodeiro C Pina F Maestri M Balzani V 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(6):1519-1526
We have investigated the network of reactions observed for the photochromic 4'-hydroxy-6-nitroflavylium compound in aqueous solutions upon pH changes (including pH jump and stopped flow experiments) and light excitation. The changes observed in the NMR and UV/Vis spectra allowed identification of ten different forms in which this compound can be transformed depending on the experimental conditions. Equilibrium and kinetic constants have been determined. Compared with other members of the flavylium family, 4'-hydroxy-6-nitroflavylium is characterized by a large cis-->trans isomerization barrier, and a very efficient hydration reaction. These peculiar features allow writing, reading, storing and erasing photonic information on 4'-hydroxy-6-nitroflavylium by a novel cyclic process that involves the following steps: write-lock/read/unlock/enable-erase/erase. 相似文献
93.
Tseng HR Vignon SA Celestre PC Stoddart JF White AJ Williams DJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(2):543-556
The template-directed syntheses, employing bisparaphenylene-[34]crown-10 (BPP34C10), 1,5-dinaphthoparaphenylene-[36]crown-10 (1/5NPPP36C10), and 1,5-dinaphtho-[38]crown-10 (1/5DNP38C10) as templates, of three [2]catenanes, whereby one of the two bipyridinium units in cyclobis(paraquat-p-phenylene) is replaced by a bipicolinium unit, are described. The crude reaction mixtures comprising the [2]catenanes all contain slightly more of the homologous [3]catenanes, wherein a "dimeric" octacationic cyclophane has the crown ether macrocycles encircling the alternating bipyridinium units with the bipicolinium units completely unfettered. X-ray crystallography, performed on all three [2]catenanes and two of the three [3]catenanes reveals co-conformational and stereochemical preferences that are stark and pronounced. Both the [3]catenanes crystallize as mixtures of diastereoisomers on account of the axial chirality associated with the picolinium units in the solid state. Dynamic (1)H NMR spectroscopy is employed to probe in solution the relative energy barriers for rotations by the phenylene and pyridinium rings in the tetracationic cyclophane component of the [2]catenanes. Where there are co-conformational changes that are stereochemically "allowed", crown ether circumrotation and rocking processes are also investigated for the relative rates of their occurrence. The outcome is one whereby the three [2]catenanes containing BPP34C10, 1/5NPPP36C10, and 1/5DNP38C10 exist as one major enantiomeric pair of diastereoisomers amongst two, four, and eight diastereoisomeric pairs of enantiomers, respectively. The diastereoisomerism is a consequence of the presence of axial chirality together with helical and/or planar chirality in the same interlocked molecule. These [2]catenanes constitute a rich reserve of new stereochemical types that might be tapped for their switching and mechanical properties. 相似文献
94.
95.
A silver(I)-saccharinato (sac) complex with nicotinamide (nia), [Ag(sac)(nia)]
n
has been synthesized and characterized by elemental analysis, IR spectroscopy, DTA-TG analyses and single crystal X-ray diffractometry. The complex crystallizes in monoclinic space group P21/n with unit cell parameters of a=7.0258(4) Å, b=24.3784(10) Å, c=8.4301(5) Å, β=109.407(5)°, V=1361.85(13) Å3 and Z=4. [Ag(sac)(nia)]
n
contains [Ag(sac)(nia)] units, which are doubly bridged by both nia and sac ligands, leading to a linear one-dimensional polymeric chains running along the a axis. The silver(I) ion has a highly distorted AgN2O2 tetrahedral geometry and the coordination polymer exhibits relatively short intra-chain ligand supported Ag···Ag separations of 3.1593(4) Å. The one-dimensional chains are crosslinked by N–H···O hydrogen bonds and aromatic π(sac)···π(nia) stacking interactions to generate a two-dimensional layer structure. IR spectra and thermal analysis data are in agreement with the crystal structure. 相似文献
96.
Inclusion complexes of poly(ethylene oxide) with α-cyclodextrin are the key compounds in the synthesis of polyrotaxanes. These
complexes prepared in aqueous solutions contain free cyclodextrin, which cocrystallizes with the major reaction product. These
complexes dissociate upon dissolution in DMF and DMSO to form cyclodextrin and pseudopolyrotaxanes with a low cyclodextrin
content. Polyrotaxane was synthesized with the use of poly(ethylene oxide)-α,ω-bis-amine as a linear component. The end-groups
of the polymer in the inclusion complex were modified by the reaction with 2,4-dinitrofluorobenzene. A procedure was developed
for purification of a polyrotaxane with high cyclodextrin content.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1914–1918, August, 2005. 相似文献
97.
Qian-Feng Zhang Yu-Jie Liu Richard D. Adams Alexander Rothenberger Dieter Fenske Wa-Hung Leung 《Journal of Cluster Science》2006,17(3):445-455
Treatment of tetracopper(I)-phosphonitocavitand [1·Cu4(μ-Cl)4(μ4-Cl)] (2) (1 = tetraphosphonitocavitand [rccc-2,8,14,20-tetrakis-(iso-butyl)-phosphonitocavitand (C44H48O8P4Ph4)]) with PhSeSiMe3 in THF at low temperature afforded a novel polyanionic cluster [pyH]6[(CuCl)9(μ3-SePh)5(μ4-SePh)] (4) as a major product along with a new tetracopper(I)-phosphonitocavitand (3) with a centered μ3-Cl. Molecular structure of anionic cluster in 4 consists of six PhSe− bridging ligands containing five μ3-SePh and one exceptional μ4-SePh bridging nine copper atoms, of which eight copper atoms have trigonal coordination geometry and the other has distorted
tetrahedral geometry.
Dedicated to Professor Han-Qin Liu on the occasion of his 70th birthday. 相似文献
98.
Klärner FG Kahlert B Boese R Bläser D Juris A Marchioni F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3363-3374
Novel molecular clips with anthracene sidewalls (1 a-c) were synthesized; they form stable host-guest complexes with a variety of electron-deficient aromatic and quinoid molecules. According to single-crystal structure analyses of clip 1 c and 1,2,4,5-tetracyanobenzene (TCNB) complex 14@1 b, the clips' anthracene sidewalls have to be compressed substantially during the complex formation to provide attractive pi-pi interactions between the aromatic guest molecule and the two anthracene sidewalls in the complex. The compression and expansion of aromatic sidewalls are calculated by molecular mechanics to be low-energy processes, so the energy required for compression of the anthracene sidewalls during complex formation is apparently overcompensated by the gain in energy resulting from the attractive pi-pi interactions. The finding that complexes of the clips 1 a-c are more stable than those of the corresponding clips 2 a-c can be explained in terms of the larger van der Waals contact surfaces of the anthracene sidewalls in 1 a-c (relative to the naphthalene sidewalls in 2 a-c). Color changes resulting from charge-transfer (CT) bands are observed in complex formation by 1 a-c: from colorless to red or purple with TCNB (14), and from yellow to green with 2,4,7-trinitro-9-fluorenone TNF (17). Independently, the host 1 b and guest 14 fluoresce from their respective excited singlet states, whilst in the complex 14@1 b the charge-transfer state quenches the higher-energy singlet states of the two components, and as a result luminescence is only observed from this new CT state. To the best of our knowledge, complex 14@1 b is the first example of CT luminescence from a host-guest complex. The binding constant determined for the formation of the TCNB complex 14@1 b from a UV/Vis titration experiment (Ka = 12 400 m(-1)) agrees well with the value (K(a) = 12 800 m(-1)) obtained by 1H NMR titration. 相似文献
99.
Binuclear Nickel(0) Alkyne Coordination Compounds – Correlation between Ligand Periphery and Supramolecular Structure Reaction of Ni(cdt: 1,5,9-cyclododecatriene) with functionalized alkynes and subsequent reaction with ethylenediamines gives binuclear compounds of the type (diamine)Ni(μ-alkyne)Ni(alkyne). Compounds with alkyne-diols (N?N)Ni2(HOR1R2C? C?C? CR1R2OH)2 show supramolecular structures in which two identical intramolecular and one intermolecular hydrogen bonds are realized. 1 and 2 (chelate ligand in each case N,N,N′,N′-tetramethylethylenediamine, TMEDA, in 1 R1 = R2 = Me, in 2 R1 = R2 = Et) polymer-like chains are built up by connecting the binuclear units. Via two intermolecular hydrogen bonds per organometallic unit in 1 and via one intermoleculare hydrogen bond in 2 the chains are connected to give double chains. By substitution of one methyl group of TMEDA by hydrogen ( 3 : R1 = R2 = Me) a polymerlike network is produced by connecting the polymer-like chains. In compound 4 in which one of the methyl groups of TMEDA is substituted by CH2CH2NMe2 the polymer-like chains remain unconnected. In 5 (diamine = TMEDA, alkyne = (CH3)3C? C?C? CMe2OH) one intermolecular hydrogen bond per organometallic unit is observed forming again polymer-like chains that are independent of each other. 相似文献
100.
Michels JJ O'Connell MJ Taylor PN Wilson JS Cacialli F Anderson HL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6167-6176
A series of conjugated polyrotaxane insulated molecular wires are synthesised by aqueous Suzuki polymerisation, using hydrophobic binding to promote threading of the cyclodextrin units. These polyrotaxanes have conjugated polymer cores based on poly(para-phenylene), polyfluorene, and poly(diphenylene-vinylene), threaded through 0.9-1.6 cyclodextrins per repeat unit. Bulky naphthalene-3,6-disulfonate endgroups prevent the macrocycles from slipping off the conjugated polymer chains. Dialysis experiments show that the cyclodextrins become unthreaded only if smaller stoppers are used. MALDI TOF mass spectra detect oligomers with up to ten threaded cyclodextrins, and reveal the presence of some defects that result for oxidative homo-coupling of boronic acids. Weight-average molecular weights were determined by analytical ultracentrifugation, demonstrating that step-growth polymerisation is efficient enough to achieve degrees of polymerisation up to approximately 20 repeat units (84 para-phenylenes). The fluorescence spectra of these polyrotaxanes indicate that the presence of the threaded cyclodextrin macrocycles reduces the flexibility of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as the smaller Stokes shift, indicate that the polyrotaxanes are more rigid than the unthreaded polymers. 相似文献