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61.
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
62.
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
63.
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
64.
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
65.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
66.
Ruojie Tao Shuangquan Zang Chongzhen Mei Qinglun Wang Benyong Lou Jingyang Niu Yanxiang Cheng Daizheng Liao 《Journal of Cluster Science》2003,14(4):459-469
Two heterometallic trinuclear complexes {[Cu(oxbp)]2Co(H2O)2}1.5DMF0.5H2O (complex 1) and {[Cu(oxbm)]2Co(H2O)2}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]– and [Cu(oxbm)]–[H3oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H3oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm–1 for complex 1 and 2, respectively. 相似文献
67.
Herein we describe the importance of side chains in C3-symmetric ligands in supramolecular chemistry. The reaction of the new ligand tris(5-bromo-2-methoxybenzylidene)triaminoguanidinium chloride [H3Me3Br3L]Cl (1) with ZnCl2 results in the formation of the monomeric complex (Et3NH)2[(ZnCl2)3Me3Br3L] (2), in which the ligand remains in a conformation less favourable for the coordination of metal centres. The use of the related tris(5-bromo-2-hydroxybenzylidene)triaminoguanidinium chloride, [H6Br3L]Cl, under similar conditions, results in the formation of two different dimeric compounds (NH4)[{[Zn(NH3)]3Br3L}2{mu-(OH)}3]1/4MeOH (3) and [Zn{Zn2(OH2)3(NH3)Br3L}2] (4), depending on the solvent mixture used. The comparable reaction of the ligand tris(5-bromo-2-hydroxy-3-methoxybenzylidene)triaminoguanidinium chloride [H6(OMe)3Br3L]Cl (5), leads to the formation of a doughnut-shaped, protein-sized coordination oligomer (Et3NH)18[{Zn[Zn2Cl{(OMe)3Br3L}]2}6(mu-Cl)6(OH2)6]x CH3CN (6), which comprises six dimeric [Zn5{(OMe)3Br3L}2] units. Whereas 3 and 4 decompose in DMSO solution, 6 is surprisingly stable in the same solvent. 相似文献
68.
T. M. Polyanskaya 《Journal of Structural Chemistry》2006,47(5):887-893
A single crystal X-ray diffraction study of a new iodine-containing cluster compound 9-(pyridine)-11-iodo-decahydro-7,8-dicarba-nido-undecaborane [9-C5H5N-11-I-7,8-C2B9H10] has been performed. Crystal data: C7H15B9NI, M = 337.39, monoclinic, space group P21/c, unit cell parameters: a = 9.348(1) Å, b = 11.159(1) Å, c = 13.442(2) Å, β = 98.13(1)°, V = 1388.1(5) Å3, Z = 4, d calc = 1.614 g/cm3, T = 295 K, F(000) = 648, μ = 2.276 mm?1. The structure was solved by a direct method and refined in the full-matrix anisotropic approximation (isotropic for hydrogen atoms) to final agreement factors R 1 = 0.0254, wR 2 = 0.0454 for 2437 I hkl ≥ 2σI from 3590 measured I hkl (an Enraf-Nonius CAD-4 diffractometer, λMoK α , graphite monochromator, θ/2θ-scanning). The molecules are joined into a supramolecular assembly by hydrogen bonds X-H?I (X = B, C). 相似文献
69.
Adachi K Sugiyama Y Yoneda K Yamada K Nozaki K Fuyuhiro A Kawata S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6616-6628
Novel triply hydrogen bonded suprastructures based on [M(tdpd)2(L)2]2- (H2tdpd=1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile, L=solvent) and melamine-analogous cations have been synthesized and characterized. The use of anions containing two AAA sets from [M(tdpd)2(L)2]2- together with cations containing one DDD set (A=hydrogen-bond acceptor, D=hydrogen-bond donor) leads to the formation of complementary triply hydrogen bonded modules in the solid state. In all cases, the building module is further extended via additional hydrogen-bonding interactions to produce a tape, and tapes are assembled into sheets. These results show that a hydrogen-bonded module consisting of different kinds of building blocks, one of which is a metal complex that includes hydrogen-bond acceptor sites and the other is a hydrogen-bond donor molecule, will be attractive for constructing metal-containing supramolecular systems by the self-assembly technique. 相似文献
70.
Jos M. J. Paulusse Rint P. Sijbesma 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5445-5453
The history of ultrasound in polymer chemistry goes back a long way. Initially, its uses were limited to being an alternative method of initiating radical polymerizations through the decomposition of solvents to form radicals or through the breakage of polymers leading to macroradicals. Recently, the raw power of ultrasound has been focused through the use of weak linkages in polymer chains, which enables the production of well‐defined macroradicals and coordinatively unsaturated metal complexes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5445–5453, 2006 相似文献