Preparation and properties of cyclodextrin inclusion compounds of organometallic complexes. Ferrocene inclusion compounds

Inclusion compounds of ferrocene(FcH) and its derivatives with cyclodextrins(CDs; -CD, -CD, and -CD) were prepared. CD-ferrocene inclusion compounds were obtained in a crystalline state in high yield. -CD and -CD formed 11 stoichiometric inclusion compounds with ferrocene and its derivatives. -CD formed 21 (CD:guest) complexes with ferrocene and the monosubstituted derivatives, but did not form complexes with 1,1-disubstituted derivatives, -CD-FcH and -CD-FcH complexes are thermally stable and do not liberate ferrocene on heating at 100°C in vacuo. The cyclodextrin inclusion compounds were characterized by¹H-NMR, IR, UV, and CD spectra. A large positive induced Cotton effect was observed in the case of -CD-FcH complex, while the -CD-FcH complex showed a negative spectrum. The binding mode is discussed. -Cyclodextrin was found to form inclusion complexes in ethylene glycol, diethylene glycol, triethylene glycol, methyl cellosolve, ethyl cellosolve, methyl alcohol, and glycerine solutions. -CD also formed complexes in ethylene glycol solution. The binding of ferrocene by -CD is stronger in ethylene glycol than in dimethyl sulfoxide and dimethyl formamide.     

The thermal decomposition of transition-metal complexes containing heterocyclic ligands: I. Benzothiazole complexes

Enthalpies of the decomposition reactions MX₂L₂(c)→MX₂(c) + 2L (g), where M is Mn, Co, Ni, Cu, or Cd, X is Cl and/or Br, and L is benzothiazole or 2-methyl-benzothiazole have been measured by use of a differential scanning calorimeter. Specific heats and enthalpies of sublimation of some of the complexes have been obtained.     

The thermal decomposition of transition-metal complexes containing heterocyclic ligands: 2.Benzoxazole complexes

Enthalpies of the overall decomposition reactions

and of the intermediate reactions involving stepwise loss of ligand, L, where M is Mn, Co, Ni, Cu, or Cd, X is Cl or Br, and L is benzoxazole, 2-methylbenzoxazole, or 2,5-dimethylbenzoxazole have been measured by use of a differential scanning calorimeter. Specific heats of CoCl₂(2-methylbenzoxazole)₂, and CoBr₂(2-methylbenzoxazole)₂ are reported together with enthalpies of sublimation of CoCl₂(2-methylbenzoxazole)₂, CoBr₂(2-methyl-benzoxazole)₂, CoCl₂(2,5-dimethylbenzoxazole)₂ and CoBr₂(2,5-dimethylbenzoxazole)₂. Enthalpies of decomposition of benzoxazole complexes are found to be greater than those of the corresponding pyridine complexes, but less than those of the analogous benzothiazole complexes. However, the mean bond dissociation energies of the cobalt—nitrogen and cobalt—oxygen bonds in these complexes are all in the region 33±2 kcal mol^?.     

Synthesis and properties of macroheterocyclic compounds containing substituted benzidine fragments

Biphenyl-4,4′-diamines and symmetric macroheterocyclic compounds were synthesized by the reaction of indan-1,3-dione with substituted benzidines (3,3′-dichloro, 3,3′-dimethoxy, 2,2′-disulfo, and 2,2′-dinitro). The products were characterized by IR and UV spectra.     

Synthesis and extraction properties of oxathiacrown compounds containing benzyl groups

8-Benzyl-1.4-dioxa-7,10-dithiacyclododecane and 11-benzyl-1,4,7-trioxa-10,13-dithiacyclopentadecane were obtained by the interaction of (2,3-dibromo-1-propyl)benzene with 1,8-dimercapto-3,6-dioxaoctane and 1,11-dimercapto-3,6,9-trioxaundecane. The extracting ability of the obtained compounds has been studied in relation to Sr²⁺ and Pb²⁺ ions from aqueous solutions in the presence of anions of various degrees of hardness with determination of the metal content by a radiometric method. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 244–249, February, 2006.     

Spectral properties and supramolecular inclusion complexes of β-cyclodextrin with flexible amphiphilic and rigid compounds

Spectral properties and inclusion complexes of β-cyclodextrin (β-CD) with nonionic amphiphiles and rigid 1-bromonaphthalene (BrN) was investigated in detail. Fluorescence and ¹H NMR measurements give new insights into inclusion of the hydrophobic moiety of amphiphiles into the cavity of β-CD. Their apparent stability constants were well correlated with the structure of the hydrophobic moiety of amphiphiles. The long and flexible hydrophobic moiety may occupy the cavity in the compressed manner. The phosphorescence quenching and the binding strength of BrN in ternary complexes indicate that the inclusion depth and the rigidity of BrN in the cavity of β-CD are predominant factors in determining its phosphorescence. Further inclusion of rigid BrN into the cavity drives the built-in phenyl group of amphiphiles to expose to bulk water phase to a greater extent. Comparative analyses of molecular sizes and models reveal that the flexible hydrocarbon chain of an amphiphile in supramolecular inclusion complexes was located inside the crowded cavity of β-CD due to the filling of rigid BrN into the cavity.     

Luminescence properties of mesoporous chromium(III) terephthalate and inclusion compounds of cluster complexes

The luminescence properties of mesoporous chromium(III) terephthalate [Cr₃O(C₈H₄O₄)₃F(H₂O)₂] (MIL-101) were discovered, and the luminescence spectra were detected at temperatures from 20 to 290 K. By the interaction of MIL-101 with solutions of anionic clusters [Mo₆Cl₁₄]^2- (Mo₆) and [Re₆S₈(CN)₆]^4- (Re₆) new hybrid materials Mo₆MIL-101 and Re₆MIL-101 were synthesized, the nanoporous framework of which contains _ca. 3.5 and 1.5 clusters per cage, respectively. The synthesized hybrid materials possess the luminescence properties different from those of the initial framework and cluster complexes.     

The thermal decomposition of transition-metal complexes containing heterocyclic ligands: 3. Substituted pyridine complexes of cobalt

Enthalpies of the overall decomposition reactions CoX₂L₂(c) → CoX₂(c)+2L(g) and of the intermediate stepwise loss of ligand, L, where X is Cl or Br, and L is 3-chloropyridine, 3-bromopyridine, 2-chloropyridine, 2-bromopyridine, or 2-methoxypyridine have been measured by use of a differential scanning calorimeter. Enthalpies of sublimation of CoCl₂(3-chloropyridine)₂, CoBr₂(3-chloropyridine)₂, CoCl₂(3-bromopyridine)₂, CoCl₂(2-chloropyridine)₂, CoCl₂(2-bromopyridine)₂, CoBr₂(2-bromopyridine)₂, CoCl₂(2-methylpyridine)₂ and CoBr₂(2-methylpyridine)₂ have been determined. Values of the cobalt-nitrogen bond dissociation energies have been calculated. Specific heats of a number of the complexes are reported.     

Synthesis and magnetic properties of novel containing 1,10-phenanthroline polymeric complexes

The polymer (DAPcTPA) was synthesized by polycondensation of 5,6-diamine-1,10-phenanthroline (DAP) with terephthaldehyde (TPA). Three polymeric complexes were first prepared from polymer (DAPcTPA) and NiSO₄, CoCl₂ or FeSO₄, respectively. The structures of polymer and complexes were characterized by IR, ¹H NMR spectra and elemental analysis. The magnetic behavior of these complexes was measured as a function of magnetic field strength (0-50 kOe) at 5 K and as a function of temperature (5-300 K) at a magnetic field strength of 30 kOe. The results show that DAPcTPA-Ni²⁺ and DAPcTPA-Co²⁺ are soft ferromagnets, while DAPcTPA-Fe²⁺ exhibits features of an antiferromagnet.     

Synthesis and magnetic properties of novel polymeric complexes containing bithiazole rings

A novel linear polymer (PFABT) containing bithiazole rings was synthesized by polycondensation of 2,2′‐diamino‐4,4′‐bithiazole (DABT) and formaldehyde. The complexes of PFABT with two transition metal ions (Fe²⁺, Cu²⁺) were prepared for the first time. The polymer was determined through FT‐IR, ¹H‐NMR and elemental analysis (EA), and the complexes were characterized by FT‐IR. The magnetic behaviors of these complexes were measured as a function of magnetic field strength (0–50 kOe) at 4 K and as a function of temperature (4–300 K) under an applied magnetic field of 30 kOe. The results show that PFABT‐Cu²⁺ is a ferromagnet while PFABT‐Fe²⁺ is an anti‐ferromagnet. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and properties of new biotin compounds containing hexyltriethylene glycol chain

The synthesis of a new halogenide containing hexyltriethylene glycol chain functionalized with biotin is reported. The general possibility of this linker to use as the building block for biotinylated compounds syntheses is demonstrated. Two biotinylated esters with different properties for useful surface modification and as fluorescence probes for proteins marking were synthesized. The properties of mentioned compounds were investigated by using surface plazmon resonance ellypsometry and fluorescence spectroscopy.     

Synthesis, structure and properties of intercalation compounds containing perfluoroalkyl groups

Synthesis, structure and properties of various layered materials containing perfluoroalkyl groups in their interlayer space were summarized. They were obtained by ion exchange method for layered materials with ion exchange capacity and by silylation technique for those possessing acidic hydroxyl groups. The orientation of perfluoroalkyl groups greatly changed depending on their contents in the layered materials. The nature of the interlayer space of them changed from hydrophilic to hydrophobic and they were well dispersed in appropriate organic solvents. Some of them formed so called nanosheet solution and film samples were prepared from it. Organic molecules were introduced into the intercalation compounds by co-adsorption or exfoliation-restacking methods. The empty space surrounded by perfluoroalky chains where organic molecules are included showed unique properties. The weak interaction between perfluoroalkyl chains and included organic molecules lead the easy diffusion of them in the interlayer space, which caused the aggregation of them or affected the distribution of isomers obtained by photochemical reaction. The low vibrational C-F bonding in perfluoroalky groups reduced radiational quenching, accordingly enhanced the fluorescence from included organic dyes.     

Synthesis and properties of mesogenic laterally fluorinated compounds containing benzoxazole unit

Series of mesogenic laterally fluorinated compounds, 2-(2′,3′-difluoro-4′-alkoxybiphenyl-4-yl)-benzoxazole derivatives (nB-Fx) bearing different substituents (H, CH₃, Cl, NO₂, coded as nB-FH, nB-FM, nB-FC and nB-FN, respectively) at 5-position, were prepared and characterised. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. nB-Fx with alkoxy chain lengths of 2 to 10 carbons exhibited enantiotropic mesophases, for which the mesophase ranges were 0°C–58°C and 0°C–71°C on heating and cooling for nB-FH, 41°C–93°C and 66°C–140°C for nB-FM, 44°C–133°C and 87°C–155°C for nB-FC, and 0°C–76°C and 0°C–95°C for nB-FN, respectively. Compared to non-fluorinated analogues, with the exception of nB-FC, fluorinated nB-Fx mainly exhibited nematic mesophase both in heating and cooling, which were attributed to the disruption of the side-to-side intermolecular packing caused by the two ortho-lateral fluoro substituents. For nB-Fx series, nB-FM, nB-FC and nB-FN exhibited a much wider mesophase range than the corresponding nB-FH series, which indicated that the substituent at benzoxazole moiety was helpful in increasing the mesophase stability. With the exception of nB-FN, the nB-Fx series displayed intense photoluminescence emission at 379–383 nm in methylene chloride solution, when it was excited at its absorption maxima.     

含吡唑配体的VIB金属羰基配合物的合成与电化学性质研究

研究了吡唑类配体与M(CO)6(M=Cr,W)的光化学反应,合成了一系列的含吡唑配体的五羰基铬钨配合物。研究了该类化合物的电化学性质。结果表明：铬系列化合物存在一对准可逆的氧化还原峰,而钨系列化合物只存在一个不可逆的氧化峰,用X射线单晶衍射测定了化合物3,4,5－三甲基吡唑五羰基铬的晶体结构。该晶体为单斜晶系,空间群为P2(1)/m,晶胞参数为a=0.9106(3)nm,b=07627(2)nm,c=0.9637(3)nm,β＝91.855(5)°,V=0.6689(3)nm^3,Z=2,R=0.042,Cr为六配位的变形八面体构型。     

Structure and spectroscopic properties of cyclodextrin inclusion complexes

We compare spectroscopic properties of higher order complexes of organic guests (e.g. naphthalene, phenols, indole, C₆₀ fullerene) with cyclodextrins (CDx) to results of molecular modeling investigations. Naphthalene 1:2 complexes with -CDx show high spectral resolution and peculiar triplet properties. Molecular simulations and calculation of the experimentally measured induced circular dichroism (ICD) provide detailed structural information.     

Instrumental analysis and molecular modelling of inclusion complexes containing artesunate

Journal of Thermal Analysis and Calorimetry - The following work experimentally and numerically investigated the thermal performance of a hybrid nanofluid, prepared by decorating a nanostructured...     

Preparation and properties of cyclodextrin-metal carbonyl inclusion compounds

One-to-one inclusion compounds were obtained in a crystalline state in high yields by treatment if ironpentacarbonyl and dimanganesedecacarbonyl with γ-cyclodextrin. These represent the first examples of cyclodextrin inclusion compounds with binary metal carbonyl complexes; the metal carbonyl complexes included in cyclodextrins are thermally more stable than the free complexes.     

Synthesis and photophysical properties of highly emissive compounds containing a dibenzosilole core

A series of new rigid rod-like molecules consisting of a dibenzosilole core, ethynylene linkages, and different aryl end-groups has been synthesized by palladium-catalyzed Sonogashira cross-coupling reactions. These compounds exhibit intense blue to green emissions with high quantum efficiencies and good thermal stabilities.     

Synthesis and structures of three 1-aminoethylidenediphosphonate compounds with transition-metal ions

Three new aminodiphosphonates, namely M(phen)(AEDPH₃)₂·4H₂O (M = Zn, (1); Ni, (2)) and Cu(phen)(AEDPH₃)₂·H₂O (4), in addition to the previously reported Co(phen)(AEDPH₃)₂·4H₂O (3), Cu(2,2′-bipy)(H₂O)(HEDPH₂)·2H₂O (5), and Cu(phen)(H₂O)(HEDPH₂)·2H₂O (6) (AEDPH₄ = 1-aminoethylidenediphosphonic acid, HEDPH₄ = 1-hydroxyethylidenediphosphonic acid, phen = 1,10-phenanthroline and 2,2′-bipy = 2,2′-bipyridyl), have been synthesized and characterized. These compounds are all synthesized at the similar condition (80 °C), whereas they illustrate different frameworks. Compounds 1, 2 and 3 are isomorphous, which contain two same chelate and one six-coordinated metal ion, and display a three-dimensional (3D) supramolecular structure through hydrogen bonds and π–π stacking interactions. Compound 4 contains a chelate and a monodentate , while the Cu ion is five-coordinated. The coordination model of Cu²⁺ in 4 is similar to that of 5 and 6. Comparing with four aminoethylidenediphosphonates, the difference of their structures is directed to the coordination model of the metal ions, while the three copper(II) diphosphonates illustrate different structures based on the deprotonized degree of the corresponding diphosphonic acids.