Synthesis, crystal structure, and thermochemical behavior of the guest-host complex [(LH2)(BF4)2 H2O] (L = racemate-5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)

The interaction between BF₃ (C₂H₅)₂Oand a racemate of 5,7,7,12,12,14-hexamethyl-l,4,8,11-tetraazacyclotetradecane (L) in the presence of air moisture leads to the complex [(LH ₂) BF₄)₂ - H₂O] (I), whose structure was determined by X-ray structure analysis and confirmed by thermogravimetric data. The crystals are monoclinic, C₁₆H₄₀B₂F₈N₄O, space group P2₁ln, a-25.570(7), b = 11.231(5), c = 8.715(4) å, α = 97.32(3)?, Z = 4, the final R value is 0.0753 for 2800 unique reflections. The structure is built from the double-charged organic cations of the tetraazamacrocycle, tetrafluoroborate anions, and water molecules (1:2:1) linked by a system of hydrogen bonds of NH...F, NH...O, and OH...F type, in which all the four macrocycle nitrogens perform the function of proton donors. The macrocycle in the complex has approximately C₂ symmetry.     

一种铜大环四胺配合物的合成与晶体结构

大环金属配合物具有较高的热力学稳定性和动力学惰性,可作为药物输送体系、肿瘤诊断、核磁共振成像增强剂等。大环化学的研究将对生命科学的发展起推动作用。大环四胺配体5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂不十四烷(简记为teta)近年来引起了广泛的关注,已有一些teta的配合物被陆续报道。本文报道配合物Cu(teta)(NO3)2的合成与晶体结构。     

Synthesis and magnetic properties of the one-dimensional linear chain structure cyano-bridged complex [Cu(teta)(H2O)2][Cu(teta) Fe(CN)6]ClO4·2H2O (teta=5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacylotetradecane)

Reaction of either K₃[Fe(CN)₆] or K₄[Fe(CN)₆] with a macrocyclic Cu^II complex, [Cu(teta)](ClO₄)₂ (teta = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacylotetradecane), in aqueous solution gave the same product as shown by spectroscopic and physicochemical characterisation. The crystal structure of the complex shows that it is a one-dimensional linear chain type heterobinuclear Fe^III–Cu^II polymer. The unit is composed of a [Cu(teta)(H₂O)₂]²⁺ cationic complex, a Fe^III–Cu^II alternate linear chain unit, a ClO ₄ ^– ion and four water molecules. The Cu atom is coordinated in a distorted octahedral arrangement by four nitrogen atoms from one teta ligand and two nitrogen atoms of the bridging cyanide groups. The Cu—N bond distances involving the cyanide bridges, 2.522(7) and 2.608(7)Å, respectively, indicate weak antiferromagnetic interactions between the Fe^III and Cu^II atoms.     

Trans --> cis isomerization of trans-[(dppm)2Ru(H)(L)][BF4] (L = P(OR)3) complexes: preparation of cis-[(dppm)2Ru(eta2-H2)(L)][BF4]2

A series of new dicationic dihydrogen complexes of ruthenium of the type cis-[(dppm)(2)Ru(eta(2)-H(2))(L)][BF(4)](2) (dppm = Ph(2)PCH(2)PPh(2); L = P(OMe)(3), P(OEt)(3), PF(O(i)Pr)(2)) have been prepared by protonating the precursor hydride complexes cis-[(dppm)(2)Ru(H)(L)][BF(4)] (L = P(OMe)(3), P(OEt)(3), P(O(i)Pr)(3)) using HBF(4).Et(2)O. The cis-[(dppm)(2)Ru(H)(L)][BF(4)] complexes were obtained from the trans hydrides via an isomerization reaction that is acid-accelerated. This isomerization reaction gives mixtures of cis and trans hydride complexes, the ratios of which depend on the cone angles of the phosphite ligands: the greater the cone angle, the greater is the amount of the cis isomer. The eta(2)-H(2) ligand in the dihydrogen complexes is labile, and the loss of H(2) was found to be reversible. The protonation reactions of the starting hydrides with trans PMe(3) or PMe(2)Ph yield mixtures of the cis and the trans hydride complexes; further addition of the acid, however, give trans-[(dppm)(2)Ru(BF(4))Cl]. The roles of the bite angles of the dppm ligand as well as the steric and the electronic properties of the monodentate phosphorus ligands in this series of complexes are discussed. X-ray crystal structures of trans-[(dppm)(2)Ru(H)(P(OMe)(3))][BF(4)], cis-[(dppm)(2)Ru(H)(P(OMe)(3))][BF(4)], and cis-[(dppm)(2)Ru(H)(P(O(i)Pr)(3))][BF(4)] complexes have been determined.     

Stabilization of germanium(IV) aquafluorocompounds in host-guest type complexes with crown ethers. synthesis,crystal structure and ir spectra of the complexes [(GeF5-H2O)2-(H2-1,10-Diaza-l 8-Crown-6)] and [(trans-GeF4 · 2H2O) · 18-Crown-6·2H2O]

Stable products have been obtained from the interaction of GeO₂-HF solution with 18-membered crown ethers, 1,10-diaza-l8-crown-6 and 18-crown 6. Complexes were characterized by X-ray analysis and IR spectroscopy. Both Ge(IV) aquafluorocompounds are isostructural with their Si analogues. It was established that in the host-guest type complexes the germanium moiety as a central atom has been stabilized in the form of octahedral complexes. The host-guest interaction occurs by means of O-H(W)...O_cr, OH...F and N-H...F hydrogen bonds.     

Crystal structure and luminescence of lanthanide monodentate complexes [Ln(C(4)N(4)H(6)O)(2)(H(2)O)(6)]Cl(3) and [Ln(C(4)N(4)H(6)O)(2)(H(2)O)(3)(NO(3))(3)] (Ln = Tb or Eu)

New eight- and nine-coordinate luminescent europium(III) and terbium(III) complexes 1-4 with carbonyl group coordination have been prepared using the monodentate ligand (L) 2,4-diamino-6-hydroxy pyrimidine and characterized by X-ray and spectroscopic methods.     

Carboxylate-bridged copper(II)-lanthanide(III) complexes [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n)(Ln = Dy,Ho, Er,Y; oda = oxydiacetate)

The hydrothermal reaction of Ln(2)O(3) (Ln = Dy and Ho), Cu(OAc)(2).2H(2)O, and oxydiacetic acid in the approximate mole ratio of 1:3:8 resulted in the formation of two new members of the isostructural series of polymers formulated as [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n), crystallizing in the hexagonal crystal system, space group P6/mcc (No. 192). Temperature-dependent magnetic susceptibilities and EPR spectra are reported for the heterometallic compounds Cu-Dy 1, Cu-Ho 2, Cu-Er 3, and Cu-Y 4. The results are discussed in terms of the structure of the compounds, the electronic properties of the lanthanide ions, and the exchange interactions between the magnetic ions.     

Photoelectron imaging of Ag(-)(H2O)x and AgOH(-)(H2O)y (x=1,2, y=0-4)

The photoelectron images of Ag(-)(H(2)O)(x) (x=1,2) and AgOH(-)(H(2)O)(y) (y=0-4) are reported. The Ag(-)(H(2)O)(1,2) anionic complexes have similar characteristics to the other two coinage metal-water complexes that can be characterized as metal atomic anion solvated by water molecules with the electron mainly localized on the metal. The vibrationally well-resolved photoelectron spectrum allows the adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of AgOH(-) to be determined as 1.18(2) and 1.24(2) eV, respectively. The AgOH(-) anion interacts more strongly with water molecules than the Ag(-) anion. The photoelectron spectra of Ag(-)(H(2)O)(x) and AgOH(-)(H(2)O)(y) show a gradual increase in ADE and VDE with increasing x and y due to the solvent stabilization.     

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1)

The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.     

硫氰酸铀铣(18-冠-6)铵(或钾)配合物的合成, 特性和结构

本文报导了硫氰酸铀铣(18-冠-6)铵和硫氰酸铀酰(18-冠-6)钾两种固体配合物的合成。由测定其物理常数及谱学数据, 确定了配合物的组成为[(C12H24O6)M]2UO2(NCS)4H2O(M=NH4, K)。X射线结构分析确定了二种单晶的结构。铵配合物属正交晶素, 空间群为Fdd2, 钾配合物属单斜晶系, 空间群为C2/c。     

Synthesis and Crystal Structure of an Ion-pair Compound: [H_2(teta)]~(2+)·[Ni(CN)_4]~(2-)·2H_2O (teta = Meso-5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane)

1INTRODUCTION The macrocyclic compounds play an important ro-le in life science and materials science[1].In recent years,teta has gained extensive attention as a raw material of crystal engineering,and its coordination behavior with metallic ion has been …     

Studies on the equilibria in Ag(I) - 1,4,8,11-tetraazacyclotetradecane and Ag(I) - 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane systems in water

Summary Protonation constants of 1,4,8,11-tetraazacyclotetradecane (T ACT) and 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (TMT ACT) (=0.1) were determined bypH-metry. The values are logK ₁=10.922, logK ₂=10.511, logK ₃=2.646, logK ₄=1.620 forT ACT, and logK ₁=9.387, logK ₂=9.050, logK ₃=2.491, logK ₄=1.380 forTMTACT. Absorption maxima of the complexes AgTA CT(NO₃)₂ and AgTMTACT(NO₃)₂ were found to be ₁=280 nm, ₂=350 nm, and ₁=290 nm, ₂=400 nm, respectively. The disproportionation constants of Ag(I) ions in the presence of the amines were determined by potentiometry: forTA CT logK _d =12.778, and forTMT ACT logK _d =11.778. The mechanisms of the electrode processes taking place in solutions of the complexes under investigation were examined by means of chronovoltamperometric and coulometric measurements. The formal potential,E _f ⁰ , of the system: AgTMT ACT ²⁺+e AgTMT ACT ⁺ is +0.450 V vs. NHE.

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Untersuchungen zu den Gleichgewichten Ag(I) -1,4,8,11-Tetraazacyclotetradekan und Ag(I) -1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradekan in Wasser

Zusammenfassung Die Protonierungskonstanten von 1,4,8,11-Tetraazacyclotetradekan (TACT) und 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradekan (TMT ACT) wurdenpH-metrisch bei =0.1 bestimmt. Folgende Werte wurden ermittelt: logK ₁=10.922, logK ₂=10.511, logK ₃=2.646, logK ₄=1.620 fürTACT und logK ₁=9.387, logK ₂=9.050, logK ₃=2.491, logK ₄=1.380 fürTMT ACT. Die Absorptionsmaxima der Komplexe AgTACT(NO₃)₂ und AgTMTACT(NO₃)₂ waren ₁=280 nm, ₂=350 nm, bzw. ₁=290 nm, ₂=400 nm. Die Disproportionierungskonstanten der Ag(I)-Ionen in Gegenwart der Amine wurden potentiometrisch bestimmt: logK _d =12.778 fürTACT und logK _d =11.778 fürTMTACT. Der Mechanismus des Elektrodenprozesses in den Komplexlösungen wurde mittels Chronovoltamperometrie und Coulometrie überprüft. Das formale PotentialE _f ⁰ des Systems AgTMT ACT ²⁺+eAgTMT ACT ⁺ ist +0.450 V gegenüber NHE.

     

A Bridged High-Spin Complex Bis-[Ni(II)( rac-5,5,7,12,12,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane)]-2,5-pyridinedicarboxylate Diperchlorate Monohydrate

A bridged high-spin complex,bis-[Ni(II)(rac-5,5,7,l2,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)]-2,5-pyridinedicarboxylate diperchlorate monohydrate has been obtained by reaction of [Ni(II)(rac-5,5,7, 12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)](ClO₄)₂ and 2,5-pyridinedicarboxylic acid in aqueousalkaline (NH₄OH) medium. C₃₉H₇₇Cl₂N₉Ni₂O₁₃, chemical formula weight 1068.42, orthorhombic, P2₁2₁2₁, a = 11 .423(3) Å,b = 14.770(6) Å, c = 31.608(7) Å, = = =90.00°, V = 5333(3) ų, Z = 4, D_calc = 1.331 g cm^-3, _calc = 0.869 mm^-1, F(000) = 2272, T = 293(2), R = 0.0870 for 2686 observed reflections [I > 2(I)]. The complexincludes two folded [Ni(rac- Me₆[14]aneN₄)]²⁺ units havingopposite diastereomeric configuration. They are bridged through a dianion of2,5-pyridinedicarboxylic acid, with one Ni-atom coordinated to the O-atom ofthe 2-carboxylic group and the pyridine N-atom (forming a 5-membered chelatering), and with the second Ni-atom coordinated to both O-atoms of the 5-carboxylic group (forming a 4-membered chelate ring). Hydrogen bonding involving macrocyclic NH groups, both 2- and 5-carboxylic groups, perchlorate anions and water molecules gives rise to the formation of an infinite supramolecular network in the title compound's crystals.     

Anion-directed crystallization of coordination polymers: syntheses and characterization of Cu(4)(2-pzc)(4)(H(2)O)(8)(Mo(8)O(26)).2H(2)O and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2-pzc = 2-pyrazinecarboxylate)

Two new copper 2-pyrazinecarboxylate (2-pzc) coordination polymers incorporating [Mo(8)O(26)](4-) and [V(10)O(28)H(4)](2-) anions were synthesized and structurally characterized: Cu(4)(2-pzc)(4))(H(2)O)(8)(Mo(8)O(26)).2H(2)O (1) and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2). Crystal data: 1, monoclinic, space group P2(1)/n, a = 11.1547(5) A, b = 13.4149(6) A, c = 15.9633(7) A, beta = 90.816(1) degrees; 2, triclinic, space group P1, a = 10.5896(10) A, b = 10.7921(10) A, c = 13.5168(13) A, alpha = 104.689(2) degrees, beta = 99.103(2) degrees, gamma = 113.419(2) degrees. Compound 1 contains [Cu(2-pzc)(H(2)O)(2)] chains charge-balanced by [Mo(8)O(26)](4-) anions. In compound 2, layers of [Cu(3)(2-pzc)(4)(H(2)O)(2)] form cavities that are filled with [V(10)O(28)H(4)](2-) anions. The magnetic properties of both compounds are described.     

Crystal structure of (C2H7N4O)2[(UO2)2)(OH)2(C2O4)(CHO2)2]

An X-ray diffraction study of the single crystals of (C₂H₇N₄O)₂[(UO₂)₂(OH)₂(C₂O₄)(CHO₂)₂] was carried out. The compound crystallizes in the triclinic system, space group $P\bar 1$ , Z = 2, a = 5.5621(8) Å, b = 8.1489(10) Å, c = 11.8757(16) Å, α = 88.866(7)°, β = 82.204(6)°, γ = 87.378(6)°, V = 532.7(1) ų, ρ_calcd = 2.988 g/cm³. The main structural units in the crystal are the [(UO₂)₂(OH)₂(C₂O₄)(CHO₂)₂)]^2? chains corresponding to the crystal chemical group A₂M ₂ ² K⁰²M ₂ ¹ (A = UO ₂ ²⁺ , M² = OH^?, K⁰² = C₂O ₄ ^2? , M¹ = CHO ₂ ^? ) of uranyl complexes. The chains are united into a three-dimensional framework through the electrostatic interaction and hydrogen bonds involving uranyl, oxalate, and hydroxyl groups, formate ions, and 1-carbamoylguanidinium cations.