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1.
A new phase transition compound,2-methoxyanilinium perchlorate-18-crown-6(1) {(oCH3OC6H4NH3)+(18-crown-6) ClO4 },has been synthesized and separated as crystals.Differential scanning calorimetry(DSC) measurements show a pair of sharp peaks at 225 K(heating) and 210 K(cooling),indicating the phase transition is first-order.Dielectric anomalies observed at 225 K(heating)and 210 K(cooling) further confirm the phase transition.The crystal structures determined at 298 K and123 K are both triclinic in P 1.The most distinct difference between room-temperature and lowtemperature structures is the order–disorder transition of the host 18-crown-6 molecule,which is the driving force of the phase transition. 相似文献
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S. Z. Kusov Yu. V. Gatilov I. Yu. Bagryanskaya G. V. Romanenko T. A. Vaganova I. K. Shundrina E. V. Malykhin 《Russian Chemical Bulletin》2010,59(2):382-390
Rods (1D assemblies) formed by alternate crown ether and arylenediamine molecules are the motif of the supramolecular architecture
of crystals of molecular associates of 18-crown-6 with tetrafluoro-1,4- and -1,3-phenylenediamines, hexafluoro-2,6- and -2,7-naphthylenediamines.
Molecules in the assemblies are arranged via H-bond predominantly between the crown ether oxygen atoms and the polyfluoroarene amino group hydrogen atoms. Influence of
the amino groups mutual arrangement and the aromatic framework size on the crystal supramolecular architecture is characterized.
Specific melting heats of the crystalline 1D assemblies of para- and pseudo-para-arylenediamines are higher than those of meta- and pseudo-meta-analogs; the associates having higher melting heats selectively crystallize from solutions of isomeric phenylene- or naphthylenediamine
mixtures. 相似文献
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Russian Journal of General Chemistry - 相似文献
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Yurij A. Simonov Alexander A. Dvorkin Marina S. Fonar Edward V. Ganin Sergei A. Kotlyar 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(1):1-14
The title compounds were prepared by treating a methanol solution of the corresponding crown ether with an aqueous solution of aminosulfuric acid.Crystals of [benzo-18-crown-6·H2NSO2OH] suitable for X-ray crystallography were obtained by recrystallization from methanol. The crystals are orthorhombic, space groupP212121,a = 14.310(7),b = 12.516(4),c = 10.890(4) Å. Refinement led to a final conventionalR value of 0.051 for 909 reflections.Crystals of [18-crown-6·H2NSO2OH] suitable for X-ray crystallography were obtained by recrystallization from acetone. They are orthorhombic, space groupP212121,a = 17.027(6),b = 14.866(5),c = 8.345(4) Å. The structure was solved by a heavy atom method and refined to an agreement value of 0.067. 相似文献
5.
Wolstenholme DJ Sirsch P Onut L Flogeras J Decken A McGrady GS 《Dalton transactions (Cambridge, England : 2003)》2011,40(33):8301-8303
The extended structures of [K(1-aza-18-crown-6)]BH(4) and its 18-crown-6 analogue exhibits significantly different primary and secondary stabilizing interactions. However, their respective ion pairs display similar cation-to-anion interactions, in spite of the differences in the nature of the crown ether ligand. 相似文献
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《Journal of Molecular Catalysis #》1993,78(3):257-261
Dibenzo-18-crown-6 ether is reduced to dicyclohexano-18-crown-6 ether under very mild conditions (room temperature and atmospheric hydrogen pressure) in the presence of rhodium salt and phase-transfer reagents. Control over the stereoselectivity of the reduction can be achieved through the proper choice of the phase-transfer agent. Moreover, at higher pressure, the stereoselectivity can be increased up to a 95/5 ratio of the syn/anti isomers of the dicyclohexano-18-crown-6 ether. 相似文献
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A. N. Chekhlov 《Russian Journal of Inorganic Chemistry》2009,54(3):467-471
A new compound, dibenzo-18-crown-6 diaqua(dibenzo-18-crown-6)potassium triiodide [K(Db18C6)(H2O)2)+ · I3− · Db18C6 (I), is synthesized and studied by X-ray crystallography. The crystals of compound I are orthorhombic: a = 22.065 ?, b = 22.140 ?, c = 9.433 ?, Z = 4, space group Pccn. Structure I is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation
to R = 0.098 for all 5974 unique reflections. Structure I contains the following asymmetric units: a half of the I3− centrosymmetric anion and two halves of the mixed equally average [K(Db18C6)(H2O)2]+ host—guest complex cation (a) and a free Db18C6 molecule, each stacked on the axes 2 of the perpendicularly averaged plane
of the eighteen-membered macroheterocycle. In complex I, both Db18C6 molecules (a and b) have a “butterfly” conformation with
approximate symmetry C
2v
.
Original Russian Text ? A.N. Chekhlov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 3, pp. 516–520. 相似文献
8.
4′,4″(5″)-(Dibenzo-18-crown-6)diarylacetohydroxamic acids were obtained by the reaction of DB18C-6 with β-nitrostyrenes under
the influence of polyphosphoric acid.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 838–840, June, 2006. 相似文献
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Masoumeh Hasani Mojtaba Shamsipur 《Journal of inclusion phenomena and macrocyclic chemistry》2004,48(3-4):135-139
Interactions of hexaaza-18-crown-6 (HA18C6) and tetraaza-14-crown-4 (TA14C4) with iodine have been investigated spectrophotometrically in chloroform solution. The observed time dependence of the charge-transfer band and subsequent formation of I3 - in solution were related to the slow transformation of the initially formed 1:1 macrocycle. I2 outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion, as follows: macrocycle + I2→fast K f macrocycle.I2 (outer complex) macrocycle.I2 (outer complex) →slow (macrocycle.I+)I- (inner complex) macrocycle.I+)I- (inner complex) + I2→slow (macrocycle.I+)I3 -. The pseudo-first-order rate constants at various temperatures for thetransformation process were evaluated from the absorbance-time data. The activation parameters (Ea, Δ H?, and Δ S?) for thetransformation were obtained from the temperature dependence of the rate constants. The stoichiometry and formation constants of the resulting EDA complexes have also been determined. It was found that the (TA14C4.I+)I3 - is more stable the (HA18C6.I+)I3 - complex in chloroform solution. 相似文献
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S. V. Demin V. I. Zhilov A. Yu. Tsivadze V. V. Yakshin O. N. Vilkova N. A. Tsarenko 《Russian Journal of Inorganic Chemistry》2006,51(10):1678-1681
The extraction of rare-earth elements (REE) by alkylated crown ethers (dibenzo-and dicyclohexano-18-crown 6; DB18C6 and DCH18C6) from acid solutions in the chloroform-water system is studied. The extraction of the REE with DCH18C6 and its alkylated derivatives in the presence of trichloroacetic acid (TCA) is far more efficient than the extraction with DB18C6 and its alkylated derivatives or when nitric or acetic acid is used instead of TCA. The distribution coefficients for the cerium metals are far higher than for the yttrium metals. The metal: crown ether ratio in the extracted complex in all cases is 1:1. 相似文献
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Alexander Y. Nazarenko Oleg I. Kronikovski Marina S. Fonari Victor C. Kravtsov Yury A. Simonov Tadeush J. Malinovski 《Supramolecular chemistry》2013,25(4):259-263
Abstract Solvent extraction of lead halides with 18-crown-6 (18C6), dicyclohexano-18-crown-6 (DC18C6, cis-syn-cis and cis-anti-cis isomers) in chloroform was studied, and the extraction constants corrected for side reactions and ionic strength effects were obtained. The compounds of the same composition as those being extracted were also isolated in crystal form. The molecular structure of the [Pb(18C6)I2] complex has been determined. Crystals are monoclinic, P21/n, a = 11.237(2), b = 10.992(2), c = 8.139(2)Å, β = 97.32(3)°, V = 997.1(7)Å3, Dcalc = 2.416(2)gcm?3, Z = 2 for the composition C12H24O6PbI2. The final R-factor is 0.043 for 558 unique reflections. The lead atom is coordinated to six oxygen atoms of the crown ether and two iodine atoms forming a hexagonal bipyramidal coordination polyhedron. The 18C6 molecule and the two halogen atoms form a hydrophobic coating for the lead atom which may be assumed to be the main reason of high extraction constants of the iodine complexes. For 10-coordinate lead ion (bidentate counter ions) the cis-syn-cis isomer of DC18C6 appears to be the best extraction reagent, while for 8-coordinate lead ion (monodentate halide anion) no difference between isomers was observed. 相似文献
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E. V. Guseva T. E. Busygina R. A. Khasanshin V. K. Polovnyak E. G. Yarkova R. A. Yusupov 《Russian Journal of General Chemistry》2004,74(10):1478-1484
Compounds of the compositions [2(18-crown-6)6(H2O)2(C2H4Cl2){Pt2+(C2H4)}(Pt2Cl10)2–], [4(18-crown-6)2(OH3)+2(OH2)2(NH3)(Pt2Cl10)2–], [(dibenzo-18-crown-6)6(H2O){Pt2+(C2H4)}(Pt2Cl10)2–], and [4(dibenzo-18-crown-6)2(OH3)+2(OH2)2(NH3)Pt2Cl10)2–] were prepared by reactions of H2PtCl6 with 18-crown-6 and dibenzo-18-crown-6.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 10, 2004, pp. 1593–1599.Original Russian Text Copyright © 2004 by Guseva, Busygina, Khasanshin, Polovnyak, Yarkova, Yusupov.This revised version was published online in April 2005 with a corrected cover date. 相似文献
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I. Ya. Postovskii I. V. Podgornaya V. A. Popova M. I. Ermakova O. V. Fedorova 《Chemistry of Heterocyclic Compounds》1981,17(11):1076-1080
New derivatives of the macrocyclic polyether dibenzo-18-crown-6 that contain formazyl groupings in the aromatic rings were synthesized. The complexing ability of the polyether ring and the formazyl groupings was studied. Complexes of two types, viz., those that contain a transition metal and those that simultaneously contain a transition metal and an alkali or alkaline earth metal, were isolated in crystalline form.DeceasedTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1479–1483, November, 1981. 相似文献
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A. N. Chekhlov 《Russian Journal of Inorganic Chemistry》2008,53(11):1763-1770
Two complexes are synthesized: diaquabromo(18-crown-6)rubidium [RbBr(18-crown-6)(H2O)2] (I) and triaqua(18-crown-6)barium dibromide monohydrate [Ba(18-crown-6)(H2O)3]2+ 2Br? · H2O (II). The orthorhombic structure of compound I (space group Pnma, a = 10.124 Å, b = 15.205 Å, c = 12.544 Å, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 Å, b = 10.315 Å, c = 14.879 Å, β = 123.23°, Z = 4) are determined by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.063 (I) and 0.042 (II) for all 2293 (I) and 3363 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK α). The complex molecule [RbBr(18-crown-6)(H2O)2] in compound I and the randomly disordered cation [Ba(18-crown-6)(H2O)3]2+ in compound II are of the host-guest type: their Rb+ or Ba2+ cation (its coordination number is nine) is located in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In structure I, the coordination polyhedron of Rb+ is a distorted hexagonal pyramid with a triple apex at the Br? ligand and two O atoms of the water molecules. In structure II, the Ba2+ polyhedron is a distorted hexagonal bipyramid with one apex at the O atom of the water molecule and the other split apex at two O atoms of water molecules. 相似文献