Structure of copper(II) complexes grown from ionic liquids – 1-ethyl-3-methylimidazolium acetate or chloride

Crystals of four new copper(II) complexes have been grown from copper(II) acetate/chloride–1-ethyl-3-methylimidazolium acetate/chloride–water systems and characterized by X-ray analysis. The first complex, bis(1-ethyl-3-methylimidazolium) tetra-μ-acetato-bis[chloridocuprate(II)], [Emim]2[Cu2(C2H3O2)4Cl2] (1) (Emim is 1-ethyl-3-methylimidazolium, C6H11N2), contains [Cu2(C2H3O2)4Cl2]2− coordination anions with a paddle-wheel structure and ionic liquid cations. Two of the synthesized complexes are one-dimensional polymers, namely catena-poly[1-ethyl-3-methylimidazolium [[tetra-μ-acetato-dicuprate(II)]-μ-chlorido] monohydrate], {[Emim][Cu2(C2H3O2)4Cl]·H2O}n (2), and catena-poly[1-ethyl-3-methylimidazolium [[tetra-μ-acetato-dicuprate(II)]-μ-acetato]], {[Emim][Cu2(C2H3O2)5]}n (3). In these compounds, the Cu2(C2H3O2)4 units with a paddle-wheel structure are connected to each other through chloride (in 2) or acetate (in 3) anions to form parallel chains, between which cations of ionic liquid are situated. The last compound, bis(1-ethyl-3-methylimidazolium) tetra-μ-acetato-bis[aquacopper(II)] tetra-μ-acetato-bis[acetatocuprate(II)] dihydrate, [Emim]2[Cu2(C2H3O2)4(H2O)2][Cu2(C2H3O2)6]·2H2O (4), contains two different binuclear coordination units (neutral and anionic), connected through hydrogen bonds between water molecules and acetate ions

Formation of Unsymmetrical Trinuclear Metallamacrocycles Based on Two Different Cone Calix[4]arene Macrocyclic Rings

A combination of tetrasulfonylcalix[4]arene (3-4H) together with a calix[4]arene dicarboxylate derivative 2-4H led, in the presence of MII(NO3)2 (M = Co, Ni, Zn), to the formation of three novel isostructural metallomacrocycles of formula [M3(DMF)2(μ3-H2O)-(2-2H)-3]. The structure of the prepared coordination compounds was studied in the solid state using single crystal/powder X-ray diffraction studies. The X-ray diffraction on single crystal revealed that the structure of the obtained supramolecular complexes is composed of a trinuclear metallic cluster [M3]+6 held between one di-deprotonated molecule of (2-2H)2− offering two carboxylate groups for binding metal cations and one tetra-deprotonated compound 34−, where four oxygen atoms, belonging to four deprotonated phenolic moieties and three oxygen atoms coming from three SO2 groups, are coordinated with the cluster core. Thus, an example of an easily reproducible molecular recognition pattern involving two different types of calix[4]arene based ligands, displaying different coordination moieties, and trinuclear metallic clusters, is reported here. In addition, it has been shown that the cone moieties of the calixarene also encapsulate solvent molecules

Towards Universal Stimuli-Responsive Drug Delivery Systems: Pillar[5]arenes Synthesis and Self-Assembly into Nanocontainers with Tetrazole Polymers

In this work, we have proposed a novel universal stimulus-sensitive nanosized polymer system based on decasubstituted macrocyclic structures—pillar[5]arenes and tetrazole-containing polymers. Decasubstituted pillar[5]arenes containing a large, good leaving tosylate, and phthalimide groups were first synthesized and characterized. Pillar[5]arenes containing primary and tertiary amino groups, capable of interacting with tetrazole-containing polymers, were obtained with high yield by removing the tosylate and phthalimide protection. According to the fluorescence spectroscopy data, a dramatic fluorescence enhancement in the pillar[5]arene/fluorescein/polymer system was observed with decreasing pH from neutral (pH = 7) to acidic (pH = 5). This indicates the destruction of associates and the release of the dye at a pH close to 5. The presented results open a broad range of opportunities for the development of new universal stimulus-sensitive drug delivery systems containing macrocycles and nontoxic tetrazole-based polymers

Aurophilic Interactions of Dimeric Bisphosphine Gold(I) Complexes Pre-Organized by the Structure of the 1,5-Diaza-3,7-Diphosphacyclooctanes

The dimeric gold(I) chloride and gold(I) iodide complexes ([L2Au]Cl2 and L2AuI2) on the scaffold of the cyclic bisphosphine, namely 1,5-diaza-3,7-diphosphacyclooctane containing α-phenylbenzyl (benzhydryl) substituents at the nitrogen atoms, were synthesized. The obtained complexes were isolated as white crystalline powders. The single crystal XRD of the obtained complexes revealed the strong aurophilic interactions between two gold(I) atoms with the Au…Au distance values of 2.9977(6) and 3.1680(5) Å. The comparison of the gold complexes, based on the N,N-diaryl- and N,N-dibenzhydryl substituted 1,5-diaza-3,7-diphosphacyclooctanes, allowed to reveal the strong impact of the initial heterocycle conformation on the realization of the aurophilic interactions, where the geometry of N,N-dibenzhydryl substituted 1,5-diaza-3,7-diphosphacyclooctane, is pre-organized for the intramolecular aurophilic interactions of the complexes. The obtained complexes exhibit a bluish-green phosphorescence (λem 505 (-Cl) and 530(-I)) in the solid state at room temperature, originated by the metal-halide centered transitions, which was confirmed by the TDDFT calculations. It was found that the aurophilic interactions are realized in the ground and in the triplet excited states of the complexes. The slighter change of the geometry of the N,N-dibenzhydryl substituted gold(I) iodide complexes, under the transition from the ground state to the excited state, in comparison with their N,N-diaryl substituted analogues, results in the reduced values of the Stokes shift of luminescence (ca. 150 nm vs. 175 nm)

Mechanism-Driven Development of <i>N</i>‑(Quinolin-8-yl)-benzamide Coupling Reactions via C–H or N–H Activation

The mechanistic details of the oxidative coupling of compounds with a number of different redox centers are investigated using N-(quinolin-8-yl)-benzamide (L) as a model substrate. The control of the chemical or electrooxidation parameters in the absence or presence of a cobalt catalyst makes it possible to obtain regioselectively different oxidative coupling products (ortho- vs para-C–H/C–H vs C–H/N–H vs N–H/N–H). The results indicate that the operative mechanism depends on the type of oxidized reaction center and the oxidant nature. Oxidation affects the para-C–H bond in quinoline or the N–H fragment or the ortho-C–H bond in the benzene substituent in the molecule. The intermediate Co(II)[L–H]2 complex and C–H-activated CoIII metallacycle with benzamide ligands, which are shown to oxidize at close potentials, have been isolated and characterized by various techniques, including X-ray diffraction and voltammetry. The strength of the oxidizing agent affects the formation of a particular product, though not acting as the determining factor. Two-electron oxidation of Co(II)[L–H]2 yields to C–N coupling, but one-electron oxidation of Co(III) leads to ortho-C–C coupling. All electrochemical reactions are performed under mild conditions at room temperature without adding special reagents (oxidants, halides, phosphines, etc.)

Complexes of Ni^II, Co^II, Zn^II, and Cu^II with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations

Four new NiII, CoII, ZnII, and CuII complexes with the promising anti-tuberculosis drug (E/Z)-N′-((5-Hydroxy-3,4-bis(hydroxymethyl)-6-methylpyridin-2-yl)methylene)-isonicotino-hydrazide (LH) were synthesized and characterized by structural methods: single-crystal X-ray diffraction, vibrational spectroscopy, and mass spectrometry. The NiII, CoII, and ZnII metal ions form only amorphous phases with various morphologies according to mass spectrometry and IR spectroscopy. The CuII forms a crystalline 1D coordination polymer with the relative formula {[CuLCl]·0.5H2O}∞1. Even though the LH ligand in the crystalline state includes a mixture of E-/Z-isomers, only the tautomeric iminol E-/Z-form is coordinated by CuII in the crystal. The copper(II) complex crystallizes in the monoclinic P21/n space group with the corresponding cell parameters a = 16.3539(11) Å, b = 12.2647(6) Å, and c = 17.4916(10) Å; α = 90°, β = 108.431(7)°, and γ = 90°. DFT calculations showed that the Z-isomer of the LH ligand in solution has the lowest formation energy due to intramolecular hydrogen bonds. According to the quantum chemical calculations, the coordination environment of the CuII atom during the transfer of the molecule into the solution remains the same as in the crystal, except for the polymeric bond, namely, distorted trigonal bipyramidal. Some of the complexes investigated can be used as effective sensors in biosystems

Porous nickel and cobalt hexanuclear ring-like clusters built from two different kind of calixarene ligands : new molecular traps for small volatile molecules

Two new isomorphous ring-like hexanuclear symmetrical coordination species ((2-2H)232M6, M = Co, Ni) presenting a hollow cyclic structure were successfully designed through the molecular recognition between the in situ generated sulfonylcalix[4]arene (3) supported trinuclear clusters and flexible macrocyclic linkers based on the low rim appended calix[4]arene diacid derivative (2-4H), demonstrating a pincer-like shape. The obtained coordination compounds have been characterized from a structural point of view in the crystalline phase, revealing the formation of internal hydrophobic voids, passing through the hexameric units, and external voids, resulting from the packing of the complexes in the lattice. A slight structural transformation was evidenced upon air-drying, leading to the closure of external voids caused by the solvent release and also the solvent mobility within the network. The ability of the obtained desolvated solid-state hexanuclear species to take up small volatile molecules like H2O, CH3C(O)CH3, MeOH and EtOH has been investigated by dynamic vapor sorption (DVS), showing their high affinity towards more polarizable molecules

(2-Hydroxy-3-Methoxybenzylidene)thiazolo[3,2-<i>a</i>]pyrimidines: Synthesis, Self-Assembly in the Crystalline Phase and Cytotoxic Activity

A series of new 2-hydroxy-3-methoxybenzylidenethiazolo[3,2-a]pyrimidines with different aryl substituents at the 5 position are synthesized and characterized by 1H/ 13C NMR and IR-spectroscopy and mass-spectrometry, as well as single crystal X-ray diffraction (SCXRD). It was demonstrated that the type of hydrogen bonding can play a key role in the chiral discrimination of these compounds in the crystalline phase. The hydrogen bond of the O–H...N type leads to 1D supramolecular heterochiral chains or conglomerate crystallization in the case of the formation of homochiral chains. The hydrogen bond of O–H...O type gave racemic dimers, which are packed into 2D supramolecular layers with a parallel or angular dimers arrangement. Halogen bonding of the N...Br or O...Br type brings a new motif into supramolecular self-assembly in the crystalline phase: the formation of 1D supramolecular homochiral chains instead 2D supramolecular layers. The study of cytotoxicity against various tumor cells in vitro was carried out. It was found that 2-hydroxy−3-methoxybenzylidenethiazolo[3,2-a]pyrimidines with 3-nitrophenyl substituent at C5 carbon atom demonstrated a high efficiency against M-HeLa (cervical adenocarcinoma) and low cytotoxicity against normal liver cells

Rational Design 2-Hydroxypropylphosphonium Salts as Cancer Cell Mitochondria-Targeted Vectors: Synthesis, Structure, and Biological Properties

It has been shown for a wide range of epoxy compounds that their interaction with triphenylphosphonium triflate occurs with a high chemoselectivity and leads to the formation of (2-hydroxypropyl)triphenylphosphonium triflates 3 substituted in the 3-position with an alkoxy, alkylcarboxyl group, or halogen, which were isolated in a high yield. Using the methodology for the disclosure of epichlorohydrin with alcohols in the presence of boron trifluoride etherate, followed by the substitution of iodine for chlorine and treatment with triphenylphosphine, 2-hydroxypropyltriphenylphosphonium iodides 4 were also obtained. The molecular and supramolecular structure of the obtained phosphonium salts was established, and their high antitumor activity was revealed in relation to duodenal adenocarcinoma. The formation of liposomal systems based on phosphonium salt 3 and L-α-phosphatidylcholine (PC) was employed for improving the bioavailability and reducing the toxicity. They were produced by the thin film rehydration method and exhibited cytotoxic properties. This rational design of phosphonium salts 3 and 4 has promising potential of new vectors for targeted delivery into mitochondria of tumor cells