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1.
M. Sc. Lotta Turunen M. Sc. Ulrike Warzok Dr. Rakesh Puttreddy Dr. Ngong Kodiah Beyeh Prof. Christoph A. Schalley Acad. Prof. Kari Rissanen 《Angewandte Chemie (International ed. in English)》2016,55(45):14033-14036
Two [N???I+???N] halogen‐bonded dimeric capsules using tetrakis(3‐pyridyl)ethylene cavitands with different lower rim alkyl chains are synthesized and analyzed in solution and the gas phase. These first examples of symmetrical dimeric capsules making use of the iodonium ion (I+) as the main connecting module are characterized by 1H NMR spectroscopy, diffusion ordered NMR spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI‐MS), and ion mobility‐mass spectrometry (TW‐IMS) experiments. The synthesis and effective halogen‐bonded dimerization proceeds through analogous dimeric capsules with [N???Ag+???N] binding motifs as the intermediates as evidenced by the X‐ray structures of (CH2Cl2)2@[ 3 a 2?Ag4?(H2O)2?OTs4] and (CH2Cl2)2@[ 3 a 2?Ag4?(H2O)4?OTs4], two structurally different capsules. 相似文献
2.
Sayuri Yonekawa Aaron M. Goodpaster Benjamin A. Abel Rodney G. Paulin Charles W. Sexton James S. Poole Bruce N. Storhoff Phillip E. Fanwick 《Journal of heterocyclic chemistry》2006,43(3):689-694
3.
Ingo Pantenburg Ingrid Müller 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(10):m427-m428
(1,4,7,10,13,16‐Hexaoxacyclooctadecane‐κ6O)potassium pentaiodide, [K(C12H24O6)]I5, obtained by slow evaporation of an ethanol solution of KI, 18‐crown‐6 and I2, contains [K(18‐crown‐6)]+ cations (Ci symmetry) and I5− anions (C2 symmetry), which are arranged in alternating layers parallel to (001). In contrast to the well known tendency of I5− ions to form chains and nets, the I5− units in the title compound are isolated. 相似文献
4.
Synthesis,properties and solid state structure of 5‐diphenylphosphino‐2‐hydroxy‐1,3‐xylyl‐18‐crown‐5
Rex A. Corbin Todd W. Crabill Bruce N. Storhoff John C. Huffman 《Journal of heterocyclic chemistry》2006,43(4):997-1001
5.
《Electroanalysis》2004,16(12):1014-1018
The transfer of sodium cation facilitated by (anthraquinone‐1‐yloxy) methane‐15‐crown‐5 (L) has been investigated at the water/1,2‐dichloroethane microinterface supported at the tip of a micropipette. The diffusion coefficient of (anthraquinone‐1‐yloxy) methane‐15‐crown‐5 obtained was (3.42±0.20)×10?6 cm2 s?1. The steady‐state voltammograms were observed for forward and backward scans due to sodium ion transfer facilitated by L with 1 : 1 stoichiometry. The mechanism corresponded to an interfacial complexation (TIC) and interfacial dissociation (TID) process. The association constant was calculated to be log βo=11.08±0.03 in the DCE phase. The association constant of other alkali metals (Li+, K+, Rb+) were also obtained. 相似文献
6.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(6):498-502
The bifunctional pyridine‐2,3‐dicarboxylic acid (H2pdc) ligand has one N atom and four O atoms, which could bind more than one AgI centre with diverse binding modes. A novel infinite one‐dimensional AgI coordination polymer, namely catena‐poly[[silver(I)‐(μ2‐pyridine‐2,3‐dicarboxylato‐κ2N :O 3)‐silver(I)‐tris(μ2‐5‐methyl‐1,3,4‐thiodiazol‐2‐amine‐κ2N :N ′)] monohydrate ethanol monosolvate], {[Ag2(C7H3NO4)(C3H5N3S)3]·H2O·C2H5OH}n , has been synthesized using H2pdc and 5‐methyl‐1,3,4‐thiadiazol‐2‐amine (tda), and characterized by single‐crystal X‐ray diffraction. One AgI atom is located in a four‐coordinated AgN4 tetrahedral geometry and the other AgI atom is in a tetrahedral AgN3O geometry. A dinuclear AgI cluster formed by three tda ligands with a paddelwheel configuration is bridged by the dianionic pdc2− ligand into a one‐dimensional coordination polymer. Interchain N—H…O hydrogen bonds extend the one‐dimensional chains into an undulating two‐dimensional sheet. The sheets are further packed into a three‐dimensional supramolecular framework by interchain N—H…O hydrogen bonds. 相似文献
7.
Fullerence C60‐cryptand 22 was prepared and successfully applied as the electric carrier in the PVC electrode membrane of a bifunctional ion‐selective electrode for cations, e.g., Ag+ ions as well as anions, e.g., I? ions. The bifunctional ion‐selective electrode based on C60‐cryptand 22 can be applied as a Silver (Ag+) ion selective electrode with an internal electrode solution of 10?3 M AgNO3 in water (pH = 6.3), or as an Iodide (I?) ion selective electrode with an acidic internal electrode solution of 10?4 M KI(aq) (pH = 2) in which the cryptand 22 is protonated, and the C60‐cryptand 22 is changed to C60‐Cryptand22–H+ and becomes an anionic electro‐carrier to absorb the I? ion. The Ag+ ion selective electrode based on C60‐cryptand 22 gave a linear response with a near‐Nernstian slope (59.5 mV decade?1) within the concentration range 10?1‐10?3 M Ag+(aq). The Ag+ ion electrode exhibited comparatively good selectivity for silver ions, over other transition‐metal ions, alkali and alkaline earth metal ions. The Ag+ ion selective electrode with good stability and reproducibility was successfully used for the titration of Ag+(aq) with Cl? ions. The Iodide (I?) Ion selective electrode based on protonated C60–cryptand22‐H+ also showed a linear response with a nearly Nernstian slope (58.5 mV decade?1) within 10?1 ‐ 10?3 M I? (aq) and exhibited good selectivity for I? ions and had small selectivity coefficients (10?2–10?3) for most of other anions, e.g., F? , OH?, CH3COO?, SO42?, CO32?, CrO42?, Cr2O72? and PO43? ions. 相似文献
8.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(9):682-687
To enable a comparison between a C—H…X hydrogen bond and a halogen bond, the structures of two fluorous‐substituted pyridinium iodide salts have been determined. 4‐[(2,2‐Difluoroethoxy)methyl]pyridinium iodide, C8H10F2NO+·I−, (1), has a –CH2OCH2CF2H substituent at the para position of the pyridinium ring and 4‐[(3‐chloro‐2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium iodide, C9H9ClF4NO+·I−, (2), has a –CH2OCH2CF2CF2Cl substituent at the para position of the pyridinium ring. In salt (1), the iodide anion is involved in one N—H…I and three C—H…I hydrogen bonds, which, together with C—H…F hydrogen bonds, link the cations and anions into a three‐dimensional network. For salt (2), the iodide anion is involved in one N—H…I hydrogen bond, two C—H…I hydrogen bonds and one C—Cl…I halogen bond; additional C—H…F and C—F…F interactions link the cations and anions into a three‐dimensional arrangement. 相似文献
9.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(6):696-702
A concise and efficient synthesis of 6‐benzimidazolyl‐5‐nitrosopyrimidines has been developed using Schiff base‐type intermediates derived from N4‐(2‐aminophenyl)‐6‐methoxy‐5‐nitrosopyrimidine‐2,4‐diamine. 6‐Methoxy‐N4‐{2‐[(4‐methylbenzylidene)amino]phenyl}‐5‐nitrosopyrimidine‐2,4‐diamine, (I), and N4‐{2‐[(ethoxymethylidene)amino]phenyl}‐6‐methoxy‐5‐nitrosopyrimidine‐2,4‐diamine, (III), both crystallize from dimethyl sulfoxide solution as the 1:1 solvates C19H18N6O2·C2H6OS, (Ia), and C14H16N6O3·C2H6OS, (IIIa), respectively. The interatomic distances in these intermediates indicate significant electronic polarization within the substituted pyrimidine system. In each of (Ia) and (IIIa), intermolecular N—H…O hydrogen bonds generate centrosymmetric four‐molecule aggregates. Oxidative ring closure of intermediate (I), effected using ammonium hexanitratocerate(IV), produced 4‐methoxy‐6‐[2‐(4‐methylphenyl‐1H‐benzimidazol‐1‐yl]‐5‐nitrosopyrimidin‐2‐amine, C19H16N6O2, (II) [Cobo et al. (2018). Private communication (CCDC 1830889). CCDC, Cambridge, England], where the extent of electronic polarization is much less than in (Ia) and (IIIa). A combination of N—H…N and C—H…O hydrogen bonds links the molecules of (II) into complex sheets. 相似文献
10.
Zhong‐Lu You Hai‐Liang Zhu 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(11):m567-m568
The title complex, [Ag2(C7H5O2)2(C18H18F2N2)]n, is a dinuclear silver(I) compound with one inversion centre between pairs of Ag atoms and another at the mid‐point of the central C—C bond in the butane‐1,4‐diamine moiety. Each of the smallest repeat units consists of two silver(I) cations, two benzoate anions and one N,N′‐bis(2‐fluorobenzylidene)butane‐1,4‐diamine Schiff base ligand. Each AgI ion is three‐coordinated in a trigonal configuration by two O atoms from two benzoate anions and one N atom from a Schiff base ligand. The di‐μ‐benzoato‐disilver(I) moieties are linked by the bridging Schiff base ligand, giving zigzag polymeric chains with an [–Ag⋯Ag—N—C—C—C—C—N–]n backbone running along the b axis. 相似文献
11.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(3):325-331
Aminopyrimidine derivatives are biologically important as they are components of nucleic acids and drugs. The crystals of two new salts, namely cytosinium 6‐chloronicotinate monohydrate, C4H6N3O+·C6H3ClNO2−·H2O, ( I ), and 5‐bromo‐6‐methylisocytosinium hydrogen sulfate (or 2‐amino‐5‐bromo‐4‐oxo‐6‐methylpyrimidinium hydrogen sulfate), C5H7BrN3O+·HSO4−, ( II ), have been prepared and characterized by single‐crystal X‐ray diffraction. The pyrimidine ring of both compounds is protonated at the imine N atom. In hydrated salt ( I ), the primary R22(8) ring motif (supramolecular heterosynthon) is formed via a pair of N—H…O(carboxylate) hydrogen bonds. The cations, anions and water molecule are hydrogen bonded through N—H…O, N—H…N, O—H…O and C—H…O hydrogen bonds, forming R22(8), R32(7) and R55(21) motifs, leading to a hydrogen‐bonded supramolecular sheet structure. The supramolecular double sheet structure is formed via water–carboxylate O—H…O hydrogen bonds and π–π interactions between the anions and the cations. In salt ( II ), the hydrogen sulfate ions are linked via O—H…O hydrogen bonds to generate zigzag chains. The aminopyrimidinium cations are embedded between these zigzag chains. Each hydrogen sulfate ion bridges two cations via pairs of N—H…O hydrogen bonds and vice versa, generating two R22(8) ring motifs (supramolecular heterosynthon). The cations also interact with one another via halogen–halogen (Br…Br) and halogen–oxygen (Br…O) interactions. 相似文献
12.
F. Rubio F. García H. D. Burrows A. A. C. C. Pais A. J. M. Valente M. J. Tapia J. M. García 《Journal of polymer science. Part A, Polymer chemistry》2007,45(9):1788-1799
The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H2O and D2O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H2O and D2O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007 相似文献
13.
14.
Various mixed liquid crystals containing crown ether‐cholesteryl liquid crystal, benzo‐15‐crown‐5‐COO‐C27H45 (B15C5‐COOCh), with various common cholesteric liquid crystals, e.g., cholesteryl chloride, cholesteryl benzoate and cholesteryl palmitate, were prepared and studied using polarizing microscopy and differential scanning calorimetry. Investigating the concentration effect of B15C5‐COOCh in mixed liquid crystals revealed that the addition of B15C5‐COOCh resulted in wider phase transition temperature ranges of these cholesteryl liquid crystals. The stability of these B15C5‐COOCh/cholesteryl mixed liquid crystals was studied using comprehensive graphic molecular modeling computer programs (Insight II and Discover) to calculate their molecular energy and stability energy. The effect of salts, e.g. Na+, Co3+, Y3+ and La3+, on the transition temperature range of the mixed liquid crystals was also investigated. The crown ether cholesteric liquid crystal B15C5‐COOCh was applied both as a surfactant and an ion transport carrier to transport metal ions through liquid membranes. Cholesteryl benzo‐15‐crown‐5 exhibited distinctive characteristics of a surfactant and the critical micellar concentration (CMC) of the surfactant was investigated by the pyrene fluorescence probe method. Cholesteryl benzo‐15‐crown‐5 was successfully applied as a good ion transport carrier (Ionophore) to transport various metal ions, e.g. Li+, Na+, La3+, Fe3+ and Co3+, through organic liquid membranes. The transport ability of the cholesteryl benzo‐15‐crown‐5 surfactant for these metal ions was in the order: Co3+ ≥ Li+ > Fe3+ > Na+ > La3+. 相似文献
15.
Kiyoshi Matsumoto Hirokazu Iida Yukio Ikemi Akira Shigeta Mitsuo Toda Naoto Hayashi Robert A Bulman 《Journal of heterocyclic chemistry》2005,42(2):191-199
Substitution on the nitrogen atom, where necessary by high‐pressure SNAr reactions, of aza‐18‐crown‐6 ethers linked to heterocyclic aromatics has extended the number of potential host compounds for Ag+. The complexation of Ag+ by the new compounds has been evaluated by liquid membrane ion transport and ion extraction experiments. The nature of the binding sites of these new host compounds for Ag+ has been assessed, in DMF/D2O (4/1), by 13C nmr titration experiments with AgClO4. 相似文献
16.
Xue Li Jian‐Min Dou Ying Liu Lan‐Ying Zhu Pei‐Ju Zheng 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(10):1185-1187
The novel PtII–dibenzo‐18‐crown‐6 (DB18C6) title complex, μ‐[tetrakis(thiocyanato‐S)platinum(II)]‐N:N′‐bis{[2,5,8,15,18,21‐hexaoxatricyclo[20.4.0.19,14]hexacosa‐1(22),9(14),10,12,23,25‐hexaene‐κ6O]potassium(I)}, [K(C20H24O6)]2[Pt(SCN)4], has been isolated and characterized by X‐ray diffraction analysis. The structure analysis shows that the complex displays a quasi‐one‐dimensional infinite chain of two [K(DB18C6)]+ complex cations and a [Pt(SCN)4]2? anion, bridged by K+?π interactions between adjacent [K(DB18C6)]+ units. 相似文献
17.
Manfredo Hrner Ivan Carlos Casagrande Herton Fenner Jrg Daniels Johannes Beck 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(10):m424-m426
In the title complex, [Au(C12H8N5O4)(C18H15P)], the coordination geometry about the AuI ion is linear, with one deprotonated 1,3‐bis(4‐nitrophenyl)triazenide ion, [O2NC6H4N=N–NC6H4NO2]−, acting as a monodentate ligand (two‐electron donor), and one neutral triphenylphosphine molecule completing the metal coordination. The triazenide ligand is almost planar (r.m.s. deviation = 0.0767 Å), with the largest interplanar angle being 11.6 (7)° between the phenyl ring of one of the terminal 4‐nitrophenyl substituents and the plane defined by the N=N—N triad. The Au—N and Au—P distances are 2.108 (5) and 2.2524 (13) Å, respectively. Pairs of molecules generated by centrosymmetry are associated into a supramolecular array via intermolecular C—H⋯O interactions, and N⋯C and N⋯O π–π interactions. 相似文献
18.
Abolfazl Semnani Mojtaba Shamsipur 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(2):99-105
The complex formation reaction between iodine and 1,7-diaza-15-crown-5 (DA15C5) has been studied spectrophotometrically in chloroform at 25°C. The resulting 1:2 (DA15C5:I2) molecular complex was formulated as (DA15C5...;I+)I
3
–
. The spectrophotometric results, as well as the conductivity measurements, revealed that the gradual release of triiodide ion from its contact ion paired form in the molecular complex into the solution is the rate determining step of the reaction. The rate constant was calculated ask=(8.8±0.2)×10–3 min–1. The formation constant of the molecular complex was evaluated from the computer fitting of the absorbance-mole ratio data as logK
f=6.89±0.09. 相似文献
19.
Raffaella Puliti Carlo Andrea Mattia Lelio Mazzarella 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(9):o582-o584
In the title compound, C27H39IN3+·I?, the acridinium system shows the usual approximate mirror symmetry about the central C?N line, and the corresponding bond lengths and angles in the two halves agree within experimental error. The alkyl chain at the ring N atom is initially perpendicular to the ring plane and then bends sharply at the fourth C atom. Pairs of centrosymmetrically related cations overlap two of their rings and the dimethylamino groups are also partly involved in the overlap. Each I? ion is involved in short‐range interactions with two cations. These interactions give rise to a 14‐membered cyclic structure, which involves pairs of cations and anions across an inversion centre. 相似文献
20.
Based on the previously reported one‐dimensional channel system [(H2O)?(DB18C6)(μ2‐H2O)2/2][(H3O)?(DB18C6)(μ2‐H2O)2/2]I3 ( 2 ), which is realized by stacking of crown ether molecules (DB18C6 = dibenzo‐18‐crown‐6), other synthetic approaches towards ionic channels and their results are presented in this paper. The “cutting out” approach using DB18C6 as scissor, applied on NaI, yields the compound [Na?(DB18C6)I(THF)][Na?(DB18C6)(H2O)2]I(THF)2(CHI3) ( 1 ), in high yield. It is based on a neutral and a cationic complex of sodium by DB18C6 linked via H‐bonding to give short chain fragments. The anion exchange approach, trying to replace I3? by Br3? leads to the intercalation of a cation into a DB18C6 chain in [(Me3NPh)(DB18C6)]Br3 ( 3 ). A similar reaction as for the synthesis of 2 , but replacing iodide with bromine, yields finally a brominated DB18C6 ligand. In the presence of iron, the compound [(H5O2)?(Br4‐DB18C6)2][FeBr4], 4 , is observed, in which a H5O2+‐cation is encapsuled by two brominated crown ether molecules. The absence of Fe and an excess of Br2 leads to the complexation of H3O+, and co‐crystallisation of bromine in [(H3O)?(Br4‐DB18C6)]Br3Br2 ( 5 ). 相似文献