A new pseudopolymorph of 5,11,17,23,29,35,41,47-octabromo-49,50,51,52,53, 54,55,56-octamethoxycalix[8]arene

Crystals of the title calixarene containing CCl4 as solvent have already been investigated [Baudry, Felix, Bavoux, Perrin, Vocanson, Dumazet-Bonnamour & Lamartine (2003). New J. Chem. pp. 1540-1543]. We present here a new pseudopolymorph of this compound, C64H 56Br8O8·2C4H8O, containing tetrahydrofuran as solvent and crystallizing in a different space group. However, the molecular conformation of both molecules is very similar. Further similarities of both structures are that the calixarene molecules are located on a centre of inversion and that the solvent molecules occupy similar positions with respect to the calixarene molecules. © 2003 International Union of Crystallography Printed in Great Britain - all rights reserved

Functionalized calix[8]arenes, synthesis and self-assembly on graphite

With the intention of building hollow tubular structures by self-assembly, we have designed and successfully synthesized a series of calix[8]arene derivatives. Their phenolic units were functionalized in p-position by various groups which are able to interact via hydrogen bonding or π-π stacking. Ethynyl, amide, urea, or imide links were chosen for the covalent attachment of these functional groups, to ensure the adjustment of an optimal distance for their interaction. Two different kinds of nanostructures selfassembled on a highly oriented pyrolytic graphite (HOPG) surface were found by scanning force microscopy: parallel aligned nanorods in which the calixarene molecules are adsorbed edge-on on the graphite, providing evidence that these calix[8]arene derivatives stack in a tubular fashion, and micrometer long fiber bundles most probably composed of many nanorods. © 2005 American Chemical Society

N-acylamidophosphinates: Structure, properties and complexation towards main group metal cations

N-Acylamidophosphinates RC(X)NHP(Y)R′2 (NAAP) and their thioanalogues (X,Y=O, S; R = Alk, Ar, CCl3, Het, NR2 2, NR2R3; R' = Ar, OAlk, OAr, SAlk, NAlk2, NHAr) contain X, Y donor atoms and amide nitrogen, which are capable of taking in complexation with metal cations. An application of NAAP complexes in supramolecular chemistry has been investigated in the last decades. Developed synthetic methods allow us to obtain N-acylamidophosphinate ligands contained multiple chelating groups or a combination of several essentially various coordinating fragments in the molecule: chelating moiety C(X)NHP(Y) and a macrocycle. The latter ligands are capable of connecting ions simultaneously by the chelating sites, and by the "guest-host" mechanism using the macrocycle. The bibliography includes 104 references. © 2006 Bentham Science Publishers Ltd

Complexes of N-thiophosphorylthioureas RNHC(S)NHP(S)(OiPr)2 (HL) (R = pyridin-2-yl, pyridin-3-yl, 6-amino-pyridin-2-yl) with copper(I): Crystal structures of Cu(PPh3)nL (n = 1, 2)

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RNHC(S)NHP(S)(OiPr)2 [R = pyridin-2-yl (HLa), pyridin-3-yl (HLb), 6-amino-pyridin-2-yl (HLc)] with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to mononuclear [Cu(PPh3)2La,b-S,S′] (1, 2) and [Cu(PPh3)Lc-S,S′] (3) complexes. Using copper(I) iodide instead of Cu(PPh3)3I, polynuclear complexes [Cun(L-S,S′)n] (4-6) were obtained. The structures of these compounds were investigated by IR, 1H, 31P{1H} NMR spectroscopy, ES-MS and elemental analyses. The crystal structures of Cu(PPh3)2Lb (2) and Cu(PPh3)Lc (3) were determined by single-crystal X-ray diffraction. © 2008 Elsevier B.V. All rights reserved

Crystal structure and dynamic behavior of [Ni{PhNHC(S)NP(S)(OPr i)2-S,S}2] complex in dichloromethane solution

The crystal structure of the complex [Ni{PhNHC(S)NP(S)(OPr i)2-S,S}2] has been determined and its behavior in dichloromethane solution investigated by NMR 31P spectroscopy. The X-ray structural analysis shows the nickel atom at the symmetry center in a distorted square-planar arrangement with trans-disposition of the ligands. The six-membered cycle NiS(1)PNCS(2) has the form of the asymmetric boat. In dichloromethane solutions of the compound four signals have been detected by 31P-{1H} NMR method. These signals are related to three diamagnetic square-planar isomers with different dispositions and conformations of two ligands in anti-orientation: trans-chair-boat (A), cis-boat-boat (B), and trans-boat-boat (C). These isomers are in slow exchange equilibria. It was shown that all these forms are in rather fast chemical exchange with minor (unobserved) paramagnetic pseudo-tetrahedral isomers (AT, B T, and CT). The thermodynamic constants of equilibria between A, B, and C as well as rate constants and activation parameters for conversion of three square-planar to respective pseudo-tetrahedral forms were calculated from the 31P-{1H} NMR data. © 2005 Elsevier Ltd. All rights reserved

N-thiophosphorylthiourea containing an aza-18-crown-6 fragment. The crystal structure of bis [N-(N′-diisopropoxythiophosphorylamidothiocarbonyl)- aza-18-crown-6]nickel(II)

N-(N′-Diisopropoxythiophosphorylamidothiocarbonyl)aza-18-crown-6 (HL) was obtained by the reaction of aza-18-crown-6 with diisopropoxythiophosphorylisothiocyanate, and its chelate with NiII was characterised using IR, 1H and 31P NMR spectroscopy and single-crystal X-ray diffraction

Supramolecular Structures Formed by Calix[8]arene Derivatives

(Equation presented) Octamethoxy calix[8]arenes substituted in the para position by amide, urea, and imide functions were synthesized from the octamethyl ether of tert-butylcalix[8]arene by ipso nitration, reduction, and acylation. Scanning force microscopy of spin coated samples on graphite suggests that these derivatives self-organize into tubular nanorods via hydrogen bonds between p-amide functions. A single-crystal X-ray structure reveals a centrosymmetric conformation for the octanitro derivative

Coordination diversity of N-phosphorylated amides and ureas towards viiib group cations

The behavior of ambidentate organophosphorus ligands is of general interest because the nature of the phosphorus-element bond influences directly on the structure of chelate complexes of these compounds. Reasons allowing the polyfunctional ligands to bind metal cations using different coordination modes, closely address the fundamental questions of chemistry, such as the nature of chemical bonding and the isomerism of coordination compounds, or the influence of the ligand structure on regioselectivity of the coordination bond formation and definition of a role of weak intramolecular interactions in the structure stabilization. In the framework of the presented review the information about ambidentate coordination properties of N-Thiophosphorylated thioamides, thioureas of common formula RC(X)NHP(Y)R'2 towards VIIIB group metal cations Co(II), Ni(II), Pt(II) and Pd(II) were summarized and discussed in comparison with organic and diphosphorus analogues: (i) N-acylamides and ureas of common formula RC(X)NHC(Y)R' (NAAU), and (ii) dichalcogenoimididiphosphinates R2P(X)NHP(Y)R'2 (IDP) (X, Y = O, S, Se).© 2008 by Nova Science Publishers, Inc. All rights reserved

Gold and Silver Complexes with the Ligands N-[Bis(isopropoxy)-thiophosphoryl]thiobenzamide and N-[Bis(isopropoxy)thiophosphoryl]-N′-phenylthiourea

Gold and silver complexes with the N-[bis(isopropoxy)-thiophosphoryl]thiobenzamide (HL1) and N-[bis(isopropoxy)-thiophosphoryl]-N′-phenylthiourea (HL2) ligands are reported, The compounds [M(HL)(PPh3)]TfO, [Ag(HL)(TfO)] and [Ag(HL)(PPh3)2]TfO were obtained by the reaction of both ligands with the corresponding trifluoromethanesulfonate salts. The (acetylacetonato)gold and -silver materials [M(acac)(PPh3)] or [Au(acac)(C6F5)2] cause deprotonation of the ligands and afford [ML(PPh3)] or [AuL(C6F 5)2], whereas the reaction of [Au(TfO)(PPh3)] with HL1 in a 2:1 molar ratio in KOH/MeOH affords [Au 2(L1)(PPh3)2]TfO, The first homoleptic anionic metal compounds [AuIL2]- are also reported. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004

Synthesis and crystal structure of complexes of bipodal thiophosphorylated thioureas with divalent transition metals

According to X-ray crystallography, the title compounds exist as metallomacrocycles in the crystal. © 2004 Elsevier Ltd. All rights reserved