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Two coordination polymers, Fe(LOBF3)(CH3COO)(CH3CN)2]n•nCH3CN and [Fe(LO−)2AgNO3BF4•CH3OH]n•1.75nCH3OH•nH2O (LO− = 3,3′-(4-(4-cyanophenyl)pyridine-2,6-diyl)bis(1-(2,6-dichlorophenyl)-1H-pyrazol-5-olate)), were obtained via a PCET-assisted process that uses the hydroxy-pyrazolyl moiety of the ligand and the iron(II) ion as sources of proton and electron, respectively. Our attempts to produce heterometallic compounds under mild conditions of reactant diffusion resulted in the first coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines to retain the core N3(L)MN3(L). Under harsh solvothermal conditions, a hydrogen atom transfer to the tetrafluoroborate anion caused the transformation of the hydroxyl groups into OBF3 in the third coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines. This PCET-assisted approach may be applicable to produce coordination polymers and metal–organic frameworks with the SCO-active core N3(L)MN3(L) formed by pyrazolone- and other hydroxy-pyridine-based ligands. [ABSTRACT FROM AUTHOR]

An X-ray diffraction study of a transesterification product of N-methyl-N-(trimethoxysilylmethyl)acetamide by 4,5-dibromobenzene-1,2-diol was carried out. It was established that the coordination polyhedron of the silicon atom in an anionic complex is a distorted octahedron disordered due to the superposition of the Δ and Λ optical isomers. The presence of various hydrogen donor groups in bis(cyclohexyl)ammonium cations, solvent ethanol molecules, and non-coordinated 4,5-dibromobenzene-1,2-diol caused the formation of H-bonded chains, while dibromobenzenediol also took part in stacking interactions. [ABSTRACT FROM AUTHOR]

Imatinib is one of the most used therapeutic agents to treat leukemia, which specifically inhibits the activity of tyrosine kinases. This polytopic molecule has been structurally characterized only in the form of its piperazin-1-ium salt (mesylate, picrate, citrate, fumarate or malonate). Herein we present the crystal structure of the freebase Imatinib which precipitated from a 1:10 mixture with arginine. The molecule realizes an extended conformation and forms infinite H-bonded chains through its amide, amine and pyrimidine groups. [ABSTRACT FROM AUTHOR]

New nanosized keplerate [{Mo6O21(H2O)6}12{Mo2O4(SeO4)}30]72− was prepared by ligand substitution in the corresponding acetate complex in the presence of ammonium selenate. Three novel keplerate-type compounds (NH4)72[{Mo6O21(H2O)6}12{Mo2O4(SeO4)}30]·250H2O (2), [C(NH2)3]72[{Mo6O21(H2O)6}12{Mo2O4(SeO4)}30]·250H2O (3) and (NH4)36(NMe2H2)36[{Mo6O21(H2O)6}12{Mo2O4(SeO4)}30]·250H2O (4) have been isolated and characterized by single crystal X-ray diffraction (SCXRD). The detailed structural analysis revealed the presence of the inverted {Mo6O21(H2O)6} pentagonal building blocks in all structures. The pore blocking effect via coordination of guanidinium cations was demonstrated by 77Se NMR and UV-vis spectroscopy in solution and by X-ray analysis in the structure of 3. All compounds were characterized by IR and Raman spectroscopy and elemental analysis. [ABSTRACT FROM AUTHOR]

Introduction of "Belok/XSA" beamline‐modernization is presented here with commissioning of a modern synchrotron beamline with unique capabilities for the structural analysis of single and polycrystalline samples. The beamline is designed to perform important tasks in modern crystallography, such as solving and refining the atomic structure using the single‐ and polycrystal method, studying the real (defective) structure, and analyzing the distribution of electron density in crystals, it is also possible to study rapidly occurring processes, for example, temperature phase transitions. Due to the speed of data accumulation and a registration over a large solid angle, the method allows to study large numbers of samples. This beamline has become extremely demanded in the chemical, biological, material science, and archaeological community in Russia. [ABSTRACT FROM AUTHOR]

The chiral methacrylate monomers with photosensitive azobenzene group possessing the orthogonal smectic A* and tilted smectic C* (Sm-C*) phases have been synthesised and characterised. The monomers have been used as functional side chains for the design of corresponding polymethacrylates. X-ray diffraction has been applied to elucidate the structure and phase behaviour of liquid-crystalline side-chain polymethacrylates with azobenzene-containing central core, chiral fragments and aliphatic spacers and tails of different length. X-ray patterns of polymethacrylates oriented fibres impose the tilted Sm-C* order as a basic structure of these materials. This is complemented by a regular pattern of small-angle diffuse spots, which implies complex positional order on the local scale and serves as a precursor for the formation of a columnar phase. The increase of the total length of the aliphatic tail and spacer of the side-chain fragments leads to formation of the tilted columnar phase (Coltilt*) with two-dimensional monoclinic lattice. For the polymer containing 10 methylene units in both, spacer and aliphatic tail, the Coltilt* precedes the formation of the Sm-C* phase. The observed structural changes are explained as due to coupling between the smectic ordering of the mesogenic side groups and the polymer backbone conformation. [ABSTRACT FROM AUTHOR]

An efficient synthesis of [1,2,5]oxadiazolo[3,4- d ]pyridazine 1,5,6-trioxides ( 1 ) from 3,4-bis(hydroxyimino)methyl)-1,2,5-oxadiazole 2-oxides using a mixture of concentrated nitric and trifluoroacetic acids has been developed. The scope of the unconventional reaction was established. The 4,7-dinitro[1,2,5]oxadiazolo[3,4- d ]pyridazine 1,5,6-trioxide 1f represents a new high energy compound, unfortunately with low thermal stability. The parent [1,2,5]oxadiazolo[3,4- d ]pyridazine 1,5,6-trioxide 1c was studied by single-crystal X-ray diffraction analysis which revealed a planar molecule with an unusually long intracyclic N N bond of 1.668(5) Å and unexpected exo -cyclic bond angles at the nitroxyl nitrogen atoms. In the crystal, the molecules of 1c are bound to each other by strong π-π stacking and C H⋯O hydrogen bonding interactions into a three-dimensional framework that results in a high crystal density of 1.833 gcm −3 . [ABSTRACT FROM AUTHOR]

A series of novel transition and rare-earth metal complexes of ( Z )-4-((1-(benzo[ d ]thiazol-2-yl)-3-methyl-5-oxo-4,5-dihydro-1 H -pyrazol-4-yl)diazenyl)-1,5-dimethyl-2-phenyl-1 H -pyrazol-3(2 H )-one (HL) were isolated and identified by FT IR, EPR, 1 H NMR, and UV–VIS spectroscopy. The crystallographic data for [Cu 2 Cl 3 (L)(H 2 O)] 2 ·1.5H 2 O· CH 2 Cl 2 were obtained. The compound exists in the form of a tetranuclear species with two different metal coordination modes. The coordination polyhedra of two cations can be described as somewhat distorted tetragonal pyramids as well as two other Cu atoms of the tetrameric molecule adopt the trigonal bipyramidal coordination. The bridging chloride ligands link differently coordinated metal cations. The quantum chemical calculations indicate the existence of a ferromagnetic exchange interaction in pairs. That is in agreement with the EPR spectrum of the substance. The complex formation constants in water-ethanol solutions were determined. [ABSTRACT FROM AUTHOR]

The thermal cyclization of 5-(2-phenoxymethylphenyl-methylene)barbituric acid and its derivatives affords 2,4,6-trioxoperhydropyrimidine-5-spiro-3′-chromanes. The reactions require no catalysts and proceed at temperatures from 118 to 240 °C depending on the substrate activity. These cyclization reactions are analogous to T-reactions of tertiary amines involving the hydride transfer. [ABSTRACT FROM AUTHOR]

C21H25NO8 , P21/n, (no. 14), a = 12.905(3) Å, b = 13.370(3) Å, c = 13.090(3) Å, β = 118.19(3)°, V = 1990.5(8) Å3, Z = 4, Rgt(F) = 0.0629, wRref(F2) = 0.1966, T = 100(2) K. [ABSTRACT FROM AUTHOR]

C16H16O7, monoclinic, P21/n (no. 14), a = 12.830(3) Å, b = 8.1101(16) Å, c = 14.900(3) Å, β = 114.88(3)°, V = 1406.5(6) Å3, Z = 4, Rgt(F) = 0.0578, wRref(F2) = 0.1799, T = 100(2) K. [ABSTRACT FROM AUTHOR]

Abiraterone (AbirOH) is an active metabolite of abiraterone acetate (AbirAc) used as a therapeutic agent against prostate cancer. A variety of its solid forms includes polymorphs of pure abiraterone, abiraterone acetate, and cocrystals of abiraterone acetate with carboxylic acids, and a pyridinium-containing (HAbirOH)+ salt as well. Herein, we present the crystal structure of (HAbirOH)Br · H2O as obtained by means of NoSpherA2 refinement applied to reveal charge density distribution for abiraterone from routine single-crystal X-ray diffraction experiment. Peculiarities of noncovalent interactions in this salt are discussed in terms of molecular Voronoi and Hirshfeld surfaces. The AbirOH packing in this salt and in previously reported solids is analyzed by means of the "Crystal Packing Similarity" tool. [ABSTRACT FROM AUTHOR]

Template condensation of nioxime, tolylboronic acid and M(II) or M(III) salts gave the iron and manganese(II) clathrochelates and the chromium(III)-centered macrobicyclic anion-radical. [Display omitted] • Condensation of nioxime and TolB(OH) 2 on Fe and Mn ions gave metal(II) clathrochelates. • That on Cr2+(3+) cations afforded the chromium(III) macrobicyclic anion-radical. • Its molecule contains two alicyclic and one ortho -benzoquinonedioximate chelates. • It did not undergo any substantial chemical transformations even in air atmosphere. • It resulted from an oxidative aromatization of one ribbed cyclohexane substituent. Template condensation of nioxime as a chelating synthon and tolylboronic acid as a cross-linking agent in the presence of M(II) or M(III) salts (M = Fe, Mn) gave the regular metal(II) clathrochelates. That with Cr(II) or Cr(III) salts afforded the stable chromium(III) macrobicyclic anion-radical with two alicyclic and one ortho -benzoquinonedioximate chelate fragments. [ABSTRACT FROM AUTHOR]

Eight new solvates of 1,1′-(1,4-phenylenebis(methylene))bis(1-pyridinium) hybrid halobismuthates were obtained from dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) solutions and structurally characterized. The thermal stability of the solvates was studied using TGA/DSC methods, and the appropriate conditions for the solvent molecule loss were defined. As a result, five new hybrid halobismuthates were prepared by the thermal decomposition of the obtained solvates. Based on the synchrotron powder X-ray diffraction data, the structure of the anionic part of the crystal products produced by the thermal decomposition of solvates was determined. The optical band gap values were defined for all the prepared products. The proposed method for obtaining new hybrid halobismuthates is prospective for the synthesis of compounds, which cannot be prepared from solutions. [ABSTRACT FROM AUTHOR]

Six new coordination polymers (CPs) of cadmium based on an extended anilate-type ligand, 4,4′-(1,4-phenylenebis(azanylylidene))bis(3,6-di-tert-butyl-2-hydroxycyclohexa-2,5-dienone) (H2L), have been synthesized. The series of coordination polymers includes [Cd(L)(DMF)] (1), 1D-CP [Cd(L)(dipy-1)]·2DMF (2A) and 2D-CP [Cd(L)(dipy-1)]·DMF (2B), [Cd2(L)2(dipy-2)(DMF)2] (3), [Cd(HL)(CH3COO)(dabco)] (4) and [Cd(L)(ur)2]·(H2L) (5) (where L – deprotonated form of H2L, DMF – N,N′-dimethylformamide, dipy-1 – 4,4′-trimethylenedipyridine, dipy-2 – 4,4′-dipyridyl, dabco – 1,4-diazabicyclo[2.2.2]octane, ur – urotropine). The crystal structure and thermal decomposition of 1D- and 2D-coordination polymers are reported. The structural diversity of the synthesized compounds was found to depend on the additional neutral donor ligands in the cadmium coordination sphere. Thus, the introduction of the flexible N-donor ligand dipy-1 into the cadmium coordination sphere leads to the formation of two types of coordination polymers (1D and 2D). The use of the rigid ligand dipy-2 promotes the formation of "honeycomb" 2D-CPs. The use of shorter N-donor ligands dabco and ur leads to linear derivatives in which the ligands being coordinated by cadmium don't act as "crosslinkers" of the chains in the network. [ABSTRACT FROM AUTHOR]

Convenient self‐assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich‐like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4‐cyclic and Si6‐condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6‐complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer‐Villiger oxidation of cyclohexanone by m‐chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ‐caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer‐Villiger oxidation reaction using the same oxidant. [ABSTRACT FROM AUTHOR]

Two series of highly luminescent yttrium(III), europium(III) and terbium(III) metal–organic frameworks containing diimine aromatic ligands and the dicarboxylate linker trans-1,4-cyclohexanedicarboxylate (chdc2−) which can be described by the general formulas [M2(bpy)2(chdc)3], where M = Y3+ (1), Eu3+ (2), and Tb3+ (3) and bpy = 2,2′-bipyridyl, and [M2(phen)2(chdc)3], where M = Y3+ (4), Eu3+ (5), and Tb3+ (6) and phen = 1,10-phenanthroline, were synthesized and characterized. All compounds are based on the same dinuclear {M2(L)2(OOCR)6} building blocks and possess a similar topology of the 3D framework with narrow pores. The chelate aromatic ligands act as efficient light-harvesting antennas for subsequent energy transfer to the emitting metal center (M = Eu3+, Tb3+) or intraligand photoemission (M = Y3+). As a result, the reported compounds display intense emission in the red (Eu3+), green (Tb3+) or blue (Y3+) regions representing three basic colors (RGB) of visible light. The measured quantum yields (QYs) of the solid-state luminescence for individual compounds were found to be 63% (1), 46% (2), 59% (3), 2.3% (4), 55% (5) and 49% (6). The drastic reduction of the luminescence efficiency for 4 is explained by the strong disorder of phen ligands. The high thermal stability (up to 300 °C) and exceptional moisture resistance of the bpy-based frameworks 1–3 were confirmed by TG and PXRD measurements. Various bimetal or trimetal compositions were also prepared for the bpy-series. The luminescence properties of these mixed-metal compounds depend on both the chemical composition and excitation wavelength (λex). Remarkably, pure white emission with color temperature = 6126 K was achieved for [Y1.68Eu0.08Tb0.24(bpy)2(chdc)3] at λex = 360 nm with QY = 20%. The reported results suggest that the obtained coordination framework series is a convenient platform for the design of highly efficient light emitting materials with tunable properties. [ABSTRACT FROM AUTHOR]

The multicomponent condensation of malononitrile, hydrogen sulfide, aldehydes, 1-(cyclopent-1-en-1-yl)pyrrolidine, and alkylating agents leads to the formation of 6,7-dihydro-5H-cyclopenta[b]pyridine derivatives. The structure of a number of heterocycles obtained on their basis was studied by X-ray structural analysis. [ABSTRACT FROM AUTHOR]

The synthesis of previously unknown nitriles, esters, and an amide of 6-alkoxy-2-alkylsulfanyl-4-methyl(4,4-dimethyl)nicotinic acid has been developed. The structure of a number of the obtained derivatives was proved by X-ray structural analysis. [ABSTRACT FROM AUTHOR]

This article provides a comprehensive overview of the synthesis and characterization of luminescent substances containing azole motifs, specifically focusing on pyrazole derivatives. The authors explore different synthetic routes and reactions with hydrazines to develop more efficient methods for the synthesis of ethynylpyrazoles and ethynylpyrazolines. They also discuss the potential applications of the synthesized compounds in medicinal, agricultural, and materials science fields. The article includes experimental results, discusses reaction mechanisms, and provides data to support their findings. This resource is valuable for library patrons conducting research on azole compounds and their applications. [Extracted from the article]

A series of new manganese complexes of general formula 32-Mn4Xn , displaying a highly-reproducible [Mn II2 Mn III2 ] cluster core formation, was observed when tetra-p-adamantylcalix[4]arene 3 was used in combination with N,N′-chelating auxiliary ligands, such as bipy (32-Mn4(bipy)2, bipy = 2,2′-bipyridyl) and phen (32-Mn4(phen)2, phen = 1,10-phenanthroline), as well as with DMF/H2O solvent molecules (32-Mn4(dmf)4, 32-Mn4(dmf)2(H2O)2), acting as O-donor coligands, in the crystalline phase. Single-crystal X-ray diffraction revealed that the involvement of auxiliary ligands in coordination with Mn-ions results in the distortion of their coordination sphere and leads to the controlled compression of the {Mn4}-cluster core of complexes. Moreover, the appearance of adamantyl groups at the upper rim of the macrocyclic backbone of 3 influences the crystalline self-assembly of obtained clusters, providing a preferable "side-to-head" orientation of the cluster molecules within the crystal, leading to the observation of relatively higher {Mn4}⋯{Mn4} distances than those revealed for the earlier reported calix[4]arene supported {Mn4} clusters. All 32-Mn4Xn clusters demonstrated ferromagnetic interactions between the metal atoms within the cluster core independent of the nature of the O-donor or N-donor auxiliary ligands. [ABSTRACT FROM AUTHOR]

[Display omitted] It has been demonstrated that formamidinium–cesium polyiodides are facile reagents for converting metallic lead into perovskite at temperatures of 20–90 °C. For the first time, a tentative phase diagram of the [HC(NH 2) 2 ]I–I 2 binary system was proposed, and sub- and supersolidus phase relations in the [HC(NH 2) 2 ]I–CsI–I 2 ternary system were discussed. [ABSTRACT FROM AUTHOR]

The multicomponent reaction of aromatic and heteroaromatic aldehydes, malonodithioamide, 1-(cyclohex-1-en-1-yl)piperidine, and alkylating reagents was studied. A wide range of new 2-(alkylsulfanyl)-4-aryl(hetaryl)-5,6,7,8-tetrahydroquinoline-3-carbonitriles were synthesized, and their molecular and crystalline structures were studied by X-ray structural analysis. [ABSTRACT FROM AUTHOR]

5,7-Substituted 1,4-diazepinoporphyrazine magnesium(ii) complexes were synthesized via Mg(ii)-alkoxide templated macrocyclization. A single crystal growth synchrotron diffraction analysis permitted what is to our knowledge the first structural characterization of a 1,4-diazepinoporphyrazine. It exists as a dimer in the solid state. In silico calculations supported by solution phase spectral studies involving a series of representative derivatives, provided insights into the factors governing dimerization of 1,4-diazepinoporphyrazines. The present 1,4-diazepinoporphyrazines serve as useful probes for understanding the determinants that guide dimer–monomer equilibria and the self-assembly of phthalocyanine derivatives. [ABSTRACT FROM AUTHOR]

Three ligand-stabilized Mg(BH 4 ) 2 –based complexes have been synthesized and evaluated as potential hydrogen storage media for portable fuel cell applications. The new borohydrides: Mg(BH 4 ) 2 × 0.5Et 2 O and Mg(BH 4 ) 2 × diglyme (diglyme – CH 3 O(CH 2 ) 2 O(CH 2 ) 2 OCH 3 ) have been synthesized and examined by X-ray single crystal diffraction method. Hydrolysis reactions of the compounds liberate hydrogen in quantities ranging from 46 to 96% of the theoretical yield. The hydrolysis of Mg(BH 4 ) 2 and other borohydrides is also accompanied by the diborane formation. The amount of liberated diborane depends on the Mg-coordination environment. To explain this fact quantum-chemical calculations have been performed. It is shown that formation of Mg-O-Mg-bridges enables the side process of diborane generation. It means that the size and denticity of the ligand directly affects the amount of released diborane. In general, the larger the ligand and the higher its denticity, the smaller is amount of diborane produced. The new compound Mg(BH 4 ) 2 × diglyme decomposes without diborane formation that allows one to be considered as a new promising chemical hydrogen storage compound for the practical usage. [ABSTRACT FROM AUTHOR]

[Display omitted] 3-[2-(Aminocarbonyl)pyridinium-1-yl]propane-1-sulfonate, a promising medicinal betain, was prepared by a one-pot synthesis with a 89% yield via N -alkylation of ethyl picolinate with 1,3-propanesultone in MeCN followed by ammonolysis. The reaction involving picolinamide in MeOH followed by the treatment with acetone afforded a novel 3,3-dimethyl- 1-oxo-2,3-dihydro-1 H -imidazo[1,5-a]pyridin-4-ium 3-methoxypropane-1-sulfonate. [ABSTRACT FROM AUTHOR]

11H-Indeno[1,2-b]quinoxalin-11-one oxime (IQ-1) and tryptanthrin-6-oxime are potent c-Jun N-terminal kinase 3 (JNK-3) inhibitors demonstrating neuroprotective, anti-inflammatory and anti-arthritic activity. However, the stereochemical configuration of the oxime carbon–nitrogen double bond (E- or Z-) in these compounds was so far unknown. In this contribution, we report the results of the determination of the double bond configuration in the solid state by single crystal X-ray diffraction and in solution by 1D and 2D NMR techniques and DFT calculations. It was found that both in the solid state and in solution, IQ-1 adopts the E-configuration stabilized by intermolecular hydrogen bonds, in contrast to previously assumed Z-configuration that could be stabilized only by an intramolecular hydrogen bond. [ABSTRACT FROM AUTHOR]

A reaction of acyl chlorides derived from 1,10-phenanthroline-2,9-dicarboxylic acids with piperazine allows the preparation of the corresponding 24-membered macrocycles in good yield. The structural and spectral properties of these new macrocyclic ligands were thoroughly investigated, revealing promising coordination properties towards f-elements (Am, Eu). It was shown that the prepared ligands can be used for selective extraction of Am(III) from alkaline–carbonate media in presence of Eu(III) with an SFAm/Eu up to 40. Their extraction efficiency is higher than calixarene-type extraction of the Am(III) and Eu(III) pair. Composition of macrocycle–metal complex with Eu(III) was investigated by luminescence and UV-vis spectroscopy. The possibility of such ligands to form complexes of L:Eu = 1:2 stoichiometry is revealed. [ABSTRACT FROM AUTHOR]

Knowledge-based approach to the design of coordination polymers with a given architecture in general requires knowledge of regularities between the local coordination of metal atoms (or polynuclear metal-containing units), coordination modes of all ligands in a complex, and the entire framework topology. The effect of the local coordination on the dimensionality and topology of the underlying nets was demonstrated on the example of 4,4′-bipyridine (bipy), 1,2-bis(4-pyridyl)ethylene (bpe) and 1,2-bis(4-pyridyl)ethane (bpa) containing copper(II) malonates. The most abundant networks were evaluated for these compounds and compared with those for previously analyzed and synthesized zinc(II)-containing analogs. Eight novel complexes, namely [Cu(bpe)(mal)]·2CH3CN, [Cu4(bipy)4(Me2mal)4(H2O)5]·3H2O, [Cu(bpe)(HMe2mal)2]·H2O, [Cu(bpe)(Me2mal)]·H2O, [Cu4(bpe)3(Et2mal)4]·5H2O, [Cu4(bpa)3(Et2mal)4]·5.5H2O, [Cu(bpe)(Amal)]·0.25H2O, and [Cu(bpa)(Amal)]·0.25H2O (H2mal = malonic acid, H2Me2mal = dimethylmalonic acid, H2Et2mal = diethylmalonic acid, H2Amal = allylmalonic acid), were synthesized and characterized. Four of them realized the square lattice topology (sql) of their underlying nets, which is highly abundant for copper(II) malonates with N,N′-containing linkers but rarely occurs in similar complexes based on other transition metals. The UV-sensitivity of the bpe-containing complexes as well as of the previously reported complex [Cu4(bpe)3(mal)4]·6H2O was studied; and [Cu4(bpe)3(mal)4]·6H2O was found to undergo a single-crystal-to-single-crystal photoinitiated [2 + 2] cycloaddition reaction to [Cu4(bpe)(tpcb)(mal)4]·6H2O (tpcb = rctt-1,2,3,4-tetrakis(pyridin-4-yl)cyclobutane). The dc-magnetic measurements of the complexes [Cu(bpe)(Me2mal)]·H2O, [Cu(bpe)(Amal)]·0.25H2O and [Cu(bpa)(Amal)]·0.25H2O indicated the presence of very weak antiferromagnetic intermolecular interactions. Using EPR spectroscopy, it was shown that the distortion of the polyhedron of the copper(II) atom corresponded to a change in the anisotropy of the g-tensor. [ABSTRACT FROM AUTHOR]

The mRubyFT is a monomeric genetically encoded fluorescent timer based on the mRuby2 fluorescent protein, which is characterized by the complete maturation of the blue form with the subsequent conversion to the red one. It has higher brightness in mammalian cells and higher photostability compared with other fluorescent timers. A high-resolution structure is a known characteristic of the mRubyFT with the red form chromophore, but structural details of its blue form remain obscure. In order to obtain insight into this, we obtained an S148I variant of the mRubyFT (mRubyFTS148I) with the blocked over time blue form of the chromophore. X-ray data at a 1.8 Å resolution allowed us to propose a chromophore conformation and its interactions with the neighboring residues. The imidazolidinone moiety of the chromophore is completely matured, being a conjugated π-system. The methine bridge is not oxidized in the blue form bringing flexibility to the phenolic moiety that manifests itself in poor electron density. Integration of these data with the results of molecular dynamic simulation disclosed that the OH group of the phenolic moiety forms a hydrogen bond with the side chain of the T163 residue. A detailed comparison of mRubyFTS148I with other available structures of the blue form of fluorescent proteins, Blue102 and mTagBFP, revealed a number of characteristic differences. Molecular dynamic simulations with the combined quantum mechanic/molecular mechanic potentials demonstrated that the blue form exists in two protonation states, anion and zwitterion, both sharing enolate tautomeric forms of the C=C–O− fragment. These two forms have similar excitation energies, as evaluated by calculations. Finally, excited state molecular dynamic simulations showed that excitation of the chromophore in both protonation states leads to the same anionic fluorescent state. The data obtained shed light on the structural features and spectral properties of the blue form of the mRubyFT timer. [ABSTRACT FROM AUTHOR]

The title compound, [Zn(C20H15N4O)2].2.5C3OH, I, was synthesized via the reaction of zinc acetate with the respective ligand and isolated as a methanol solvate, i.e., as I.2.5C3OH. The crystal structure is triclinic (space group P1¯), with two complex molecules (A and B) and five methanol solvent molecules in the asymmetric unit. One of the five methanol solvent molecules is disordered over two sets of sites, with an occupancy ratio of 0.75:0.25. Molecules A and B are conformers and distinguished by the conformations of the bidentate 1-phenyl-3-methyl-4-[(quinolin-3-yl)iminomethyl]-1H-pyrazol-5-olate ligands. In both molecules, the zinc cations have distorted tetrahedral coordination spheres, binding the monoanionic ligands through the pyrazololate O and imine N atoms. The two ligands adopt slightly different conformations in terms of the orientation of the terminal phenyl and quinoline substituents with respect to the central pyrazololate moiety. The molecular geometries of A and B are supported by intramolecular C-H. . .O and C-H. . .N hydrogen bonds. In the crystal of I, molecules form dimers both by secondary intermolecular Zn. . .O [3.140 (2)- 3.553 (3) Å ] and .π-π. stacking interactions. The dimers are linked by intermolecular hydrogen bonds through the solvent methanol molecules into a three-dimensional network. [ABSTRACT FROM AUTHOR]

A series of novel metal complexes of Cu(II), Co(II), Ni(II), and Zn(II) with three N-heterocyclic derivatives of 4-azo-pyrazol-5-one were isolated and identified by FT IR, 1H NMR, ESR, and UV–Vis spectroscopy. The crystallographic data for a sodium salt as well as Co(II) and Cu(II) complexes were obtained. Formation constants of the complexes in ethanol aqueous solutions were calculated. Structures of yet unstudied metal complexes were proposed based on quantum-chemical modeling at the DFT/B3LYP level. [ABSTRACT FROM AUTHOR]

Reaction of arylglyoxal oximes ArCOCH=NOH (Ar = 4-MeOC 6 H 4 , Ph) with 5-arylfurazanopyrazines proceeds as vicarious nucleophilic substitution of hydrogen in pyrazine ring with the elimination of hyponitrous acid, affording 5-(aroylmethylidene)-6-aryl-4 H -furazano[3,4- b ]pyrazines. Structure of the product was confirmed by X-ray diffraction. [ABSTRACT FROM AUTHOR]

The coordination-driven design and synthesis of new stable supramolecular cluster–porphyrin (CP) hybrids based on an A2-type ruthenium porphyrin 5,15-bis[(p-tolyl)porphyrinato(2-)]ruthenium(carbonyl)(aqua) [RuDTolP(CO)H2O] and an octahedral molybdenum(II) iodide cluster with six terminal isonicotinate ligands (Bu4N)2[{Mo6I8}(OOC-C5H4N)6] (PyMoC) are reported. The stepwise supramolecular assembly of the PyMoC "superoctahedron" with RuDTolP(CO)H2O has been studied by 1H NMR and 2D 1H–1H COSY, 1H–15N HMBC and DOSY techniques, as well as by UV-vis spectroscopy and HR-ESI mass spectrometry. The formation of discrete cluster–porphyrin CPn adducts with different numbers of coordinated porphyrins (n = 1–6), including the geometrical isomers of CP2, CP3 and CP4, has been observed. Using a double equivalent amount of RuDTolP(CO)H2O relative to the cluster (C : P ratio 1 : 12) affords a mixture of CP5 and CP6 species in solution, while only the CP6 complex is crystallized from this system. Fine tuning of crystallization conditions leads to the formation of a more complex architecture CP6+2, where the CP6 assembly incorporates two additional porphyrin molecules bound to the cluster core by hydrogen bonds. Thus, the coordination-based supramolecular approach provides new stable cluster–multiporphyrin 3D arrays based on two types of photosensitizers, which can be promising for the design of photoactive materials. [ABSTRACT FROM AUTHOR]

A multistep general synthetic strategy towards polytopic carboranyl-containing (semi)clathrochelate metal complexes, based on the template synthesis, transmetallation, amide condensation and 1,3-dipolar cycloaddition reactions, is developed. Their mono(semi)clathrochelate precursors with a single reactive group were obtained using a transmetallation of the triethylantimony-capped macrobicyclic precursor. The thus obtained carboxyl-terminated iron(II) semiclathrochelate underwent a macrobicyclization with zirconium(IV) phthalocyaninate to form the corresponding phthalocyaninatoclathrochelate. The direct one-pot template condensation of the suitable chelating and cross-linking ligand synthons on the Fe2+ ion as a matrix was also used for its preparation. Further amide condensation of the aforementioned semiclathrochelate and hybrid complexes with propargylamine in the presence of carbonyldiimidazole gave the (pseudo)cage derivatives with a terminal C≡C bond. Their "click" reaction with an appropriate carboranylmethyl azide afforded the ditopic carboranosemiclathrochelates and the tritopic carboranyl-containing phthalocyaninatoclathrochelates with a flexible spacer fragment between their polyhedral entities. The obtained new complexes were characterized using elemental analysis, MALDI-TOF mass spectrometry, multinuclear NMR, and UV-vis spectroscopy, and by single crystal X-ray diffraction experiments. Their FeN6-coordination polyhedra show a truncated trigonal-pyramidal geometry, while the cross-linking heptacoordinate Zr4+ or Hf4+ cations in the hybrid compounds form the MIVN4O3-coordination polyhedra with the geometry of a capped trigonal prism. [ABSTRACT FROM AUTHOR]

A series of phenylsilsesquioxane-benzoate heptacopper complexes 1–3 were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2–3 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 °C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols. [ABSTRACT FROM AUTHOR]

The reproducible formation, in mild conditions, of three new 1D zigzag coordination polymers using sulfonylcalix[4]arene (TCASO2), metal M2+ cations (M=Co or Zn) and rigid planar N‐shaped linkers (stilbene‐4,4′‐dicarboxylic acid (1‐2H) or azobenzene‐4,4′‐dicarboxylic acid (2‐2H)) is reported. The obtained coordination compounds (1‐TCASO2Zn3, 1‐TCASO2Co3 and 2‐TCASO2Zn3) are characterized in the crystalline phase using single crystal and powder X‐ray diffraction (XRD and XRPD), TGA and IR‐spectroscopy. The three compounds present the same coordination pattern and 1‐TCASO2Zn3 and 2‐TCASO2Zn3 reveal to be isostructural. Due to a high porosity and amount of accommodated solvent molecules hosted in the network, the generated rigid 1D chains are capable to undergo a reversible dynamic solid‐state transformation in terms of crystal packing, accompanied with release/uptake of DMSO molecules leading to compression/stretching of the unit cell along one of the crystallographic axis which was attested by Rietveld refinement on XRPD data. [ABSTRACT FROM AUTHOR]

A series of new thiazolo[3,2-a]pyrimidines different by aryl substituents in 2 and 5 positions are synthesized and characterized in solution as well as in the crystalline phase using 1H and 13C NMR-, IR-spectroscopies, mass-spectrometry methods, and single crystal X-ray diffraction (SCXRD). The SCXRD study revealed the role of intermolecular H-bonding in the formation of supramolecular architectures (racemic monomers, centrosymmetric racematic dimers, or homochiral 1D chains) of obtained thiazolo[3,2-a]pyrimidines derivatives depending on solvents (aprotic DMSO or protic EtOH) used upon the crystallization process. Moreover, the in vitro study of cytotoxicity toward different tumor cells showed their high or moderate efficiency with moderate cytotoxicity against normal liver cells which allows to consider the obtained thiazolo[3,2-a]pyrimidine derivatives as promising candidates for application as antitumor agents. [ABSTRACT FROM AUTHOR]

The synthesis of the products of the 1,3-propanesultone ring opening during its interaction with amides of pyridinecarboxylic acids has been carried out. The dependence of the yield of the reaction products on the position (ortho-, meta-, para-) of the substituent in the heteroaromatic fragment and temperature condition was revealed. In contrast to the meta- and para-substituted substrates, the reaction involving ortho-derivatives at the boiling point of methanol unexpectedly led to the formation of a salt. On the basis of spectroscopic, X-Ray, and quantum-chemical calculation data, a model of the transition-state, as well as a mechanism for this alkylation reaction of pyridine carboxamides with sultone were proposed in order to explain the higher yields obtained with the nicotinamide and its N-methyl analog compared to ortho or meta parents. Based on the analysis of ESP maps, the positions of the binding sites of reagents with a potential complexing agent in space were determined. The in silico evaluation of possible biological activity showed that the synthetized compounds revealed some promising pharmacological effects and low acute toxicity. [ABSTRACT FROM AUTHOR]

The isomeric title compounds, C12H13NO4 (Ia) and C12H13NO4 (IIa), the products of an usual thermal C6-epimerization of 5-oxo-1,2,3,5,5a,6,7,9boctahydro- 7,9a-epoxypyrrolo[2,1-a]isoindole-6-carboxylic acid, represent the two different diastereomers and have very similar molecular geometries. The molecules of both compounds comprise a fused tetracyclic system containing four five-membered rings (pyrrolidine, pyrrolidinone, dihydrofuran and tetrahydrofuran), all of which adopt the usual envelope conformations. The dihedral angle between the basal planes of the pyrrolidine and pyrrolidinone rings are 14.3 (2) and 16.50 (11)°, respectively, for (Ia) and (IIa). The nitrogen atom has a slightly pyramidalized geometry [bond-angle sum = 355.9 and 355.3°, for (Ia) and (IIa)], respectively. In the crystal of (Ia), molecules form zigzag-like hydrogen-bonded chains along [010] through strong O--H...O hydrogen bonds and are further linked by weak C--H...O hydrogen bonds into complex twotier layers parallel to (100). Unlike (Ia), the crystal of (IIa) contains centrosymmetric cyclic hydrogen-bonded dimers [graph set R2²(14)], formed through strong O--H...O hydrogen bonds and are further linked by weak C-- H...O hydrogen bonds into ribbons extending across [101]. [ABSTRACT FROM AUTHOR]

In this work a new donor of nitric oxide (NO) with antibacterial properties, namely nitrosyl iron complex of [Fe(C6H5C-SNH2)2(NO)2][Fe(C6H5C-SNH2)(S2O3)(NO)2] composition (complex I), has been synthesized and studied. Complex I was produced by the reduction of the aqueous solution of [Fe2(S2O3)2(NO)2]2− dianion by the thiosulfate, with the further treatment of the mixture by the acidified alcohol solution of thiobenzamide. Based on the structural study of I (X-ray analysis, quantum chemical calculations by NBO and QTAIM methods in the frame of DFT), the data were obtained on the presence of the NO...NO interactions, which stabilize the DNIC dimer in the solid phase. The conformation properties, electronic structure and free energies of complex I hydration were studied using B3LYP functional and the set of 6–31 + G(d,p) basis functions. The effect of an aquatic surrounding was taken into account in the frame of a polarized continuous model (PCM). The NO-donating activity of complex I was studied by the amperometry method using an "amiNO-700" sensor electrode of the "inNO Nitric Oxide Measuring System". The antibacterial activity of I was studied on gram-negative (Escherichia coli) and gram-positive (Micrococcus luteus) bacteria. Cytotoxicity was studied using Vero cells. Complex I was found to exhibit antibacterial activity comparable to that of antibiotics, and moderate toxicity to Vero cells. [ABSTRACT FROM AUTHOR]

The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1–9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1–9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7–9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: General and straightforward synthetic strategy towards the iron(II) clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed. Their hexachloroclathrochelate precursors were prepared by the direct template condensation of dichloroglyoxime with a suitable boronic acid on the Fe2+ ion as a matrix and underwent a stepwise nucleophilic substitution with S2‐, N2‐ or O2‐bis‐nucleophiles, forming the alicyclic or aromatic N2‐, S2‐ or O2‐six‐membered fragments. Depending on the reaction conditions and precursor‐to‐dinucleophile molar ratios, iron(II) clathrochelates with one (S, O and N), two (S, O and N) or three (S and O) X2‐six‐membered ribbed substituent(s) were obtained. Their reactivity substantially decreases in a row: Cl6‐Cage > Cl4X2‐Cage (where X = S, O or, especially, N) > Cl2X4‐Cage (where X = S or O). The reactive monoribbed‐functionalized clathrochelates underwent further chemical transformations giving the target macrobicyclic complexes with terminal vector groups. As follows from the single crystal XRD data, their FeN6‐coordination polyhedra possess the geometry intermediate between a trigonal prism and a trigonal antiprism (φ = 21.3°—25.20°). Fe—N distances vary from 1.887(6) to 1.933(8) Å. Their 3D‐molecules, the hydrophobic–hydrophilic balance in which can be tuned using a ribbed functionalization, form in the crystals the intermolecular specific halogen bonds and/or hydrophobic interactions. [ABSTRACT FROM AUTHOR]

Binuclear FeII, ZrIV(HfIV)-containing phthalocyaninatoclathrochelates with a terminal reactive formyl group were prepared using three synthetic approaches, (i) the direct template condensation of appropriate chelating and capping ligand synthons on the iron(II) ion as a matrix, (ii) a transmetallation of the initially obtained macrobicyclic precursors with labile capping fragment(s), and (iii) a macrobicyclization of the suitable semiclathrochelate intermediates. The latter pathway was found to be the most favorable synthetic approach, typically giving the target hybrid compound in its highest yield. The single terminal formyl group of the thus obtained iron(II) phthalocyaninatoclathrochelates was functionalized using a post-synthetic strategy via a hydrazonate condensation with isoniazid, giving the corresponding cage complex with a biorelevant pharmacophoric fragment. These binuclear compounds and their semiclathrochelate precursors were characterized using elemental analysis, MALDI-TOF mass spectrometry, UV-vis, 1H and 13C {1H} NMR spectroscopirs, and the single crystal X-ray diffraction experiments. The ditopic hybrid molecules contain two relatively independent chromophoric centers (i.e., a metallo(IV)phthalocyaninate core and a semiclathrochelate iron(II)-centered tris-α-dioximate fragment). As follows from XRD data, the geometry of their FeN6-polyhedra is close to intermediate between a trigonal prism (the distortion angle ϕ = 0°) and a trigonal antiprism (ϕ = 60°). The capping heptacoordinate metal(IV) ions form their MIVN4O3-coordination polyhedra and are shifted from the mean plane of a phthalocyanine macrocycle at a distance from 0.9 to 1.2 Å. The developed multistep synthetic approach is proposed as a general convenient and straightforward strategy for obtaining a wide range of binuclear hybrid cage complexes of this type, functionalized for their target delivery to various biosystems (biotargets). [ABSTRACT FROM AUTHOR]

This paper presents the design and a comparative analysis of the structural and solvation factors on the spectral and biological properties of the BODIPY biomarker with a thioterpene fragment. Covalent binding of the thioterpene moiety to the butanoic acid residue of meso-substituted BODIPY was carried out to find out the membranotropic effect of conjugate to erythrocytes, and to assess the possibilities of its practical application in bioimaging. The molecular structure of the conjugate was confirmed via X-ray, UV/vis-, NMR-, and MS-spectra. It was found that dye demonstrates high photostability and high fluorescence quantum yield (to ~100%) at 514–519 nm. In addition, the marker was shown to effectively penetrate the erythrocytes membrane in the absence of erythrotoxicity. The conjugation of BODIPY with thioterpenoid is an excellent way to increase affinity dyes to biostructures, including blood components. [ABSTRACT FROM AUTHOR]

[Display omitted] • MOF with benzo-2,1,3-thiazole units shows a high 74 % luminescence quantum yield. • MOF demonstrates luminescence quenching response to gossypol in cottonseed oil. • gossypol detection in sunflower oil allows to detect oil adulteration. A new 3D metal–organic framework {[Cd 16 (tr 2 btd) 10 (dcdps) 16 (H 2 O) 3 (EtOH)]∙15DMF} n (MOF 1 , tr 2 btd = 4,7-di(1,2,4-triazol-1-yl)benzo-2,1,3-thiadiazole, H 2 dcdps = 4,4′-sulfonyldibenzoic acid) was obtained and its luminescent properties were studied. MOF 1 exhibited bright blue-green luminescence with a high quantum yield of 74 % and luminescence quenching response to a toxic natural polyphenol gossypol and luminescence enhancement response to some trivalent metal cations (Fe3+, Cr3+, Al3+ and Ga3+). The limit of gossypol detection was 0.20 µM and the determination was not interfered by the components of the cottonseed oil. The limit of detection of gallium(III) was 1.1 µM. It was demonstrated that MOF 1 may be used for distinguishing between the genuine sunflower oil and oil adulterated by crude cottonseed oil through qualitative luminescent and quantitative visual gossypol determination. [ABSTRACT FROM AUTHOR]

Here we present a new family of seven Sc(III) complexes with a tetrafluoroterephthalate ligand (tFBDC2−), having non-polymeric and polymeric 2D and 3D structures. These complexes are characterized by SC XRD, PXRD, FT-IR, elemental analysis, and TGA. Among these complexes, 3D coordination polymers [Sc(H2O)(tFBDC)1.5]·H2O (1), [Sc2(H2O)2(tFBDC)3]·2H2O (2), and [Sc(H2O)(tFBDC)1.5]·4H2O (3) are supramolecular isomers. Complex 1 is obtained as a phase pure material, while 2 and 3 are found as admixtures. The reaction of Sc(CF3SO3)3 with H2tFBDC in the presence of NH3 as a base produces layered coordination polymer [Sc(H2O)(OH)(tFBDC)] (4). Complexes (NH4)[Sc(H2O)4(tFBDC)2]·5H2O (5), [K(H2O)2Sc(H2O)4(tFBDC)2]·3H2O (6) and [Cs(H2O)4Sc(H2O)4(tFBDC)2]·0.5H2O (7) based on the same [Sc(H2O)4(tFBDC)2]− anionic unit are obtained by precipitation with NH3, KOH or CsOH. Coordination polymers 1 and 4 are stable in an aqueous solution in the range of pH 2–12. Solid complexes 1, 4–7 show ligand-centred purple/blue photoluminescence, with 1 and 4 having high quantum yields of 28 and 34% at room temperature. [ABSTRACT FROM AUTHOR]

The building of new supramolecular coordination containers, obtained through the linking of tetrasulfonylcalix[4]arene (3-4H) based transition metal tetra- or trinuclear clusters with succinic acid (suc), as a flexible aliphatic connector possessing high conformational mobility and rotational freedom, produced a variety of three different polynuclear species in the crystalline phase, which were characterized by single crystal and powder X-ray diffraction. In the case of CoII and NiII cations, the formation of unique chiral-induced isomorphous supramolecular architectures, generated by interconnection of dimeric M8-cages with the co-crystallized M(OH)2DMF4 neutral species via H-bonding, was observed. Moreover, it was found that, in contrast to what was observed with NiII cations, the use of cobalt(II) ions in the same multicomponent system, led to the formation of achiral M8-cages which were characterized by the presence of both left- and right-handed succinic acid moieties within the supramolecular entity structure. Finally, the coordination of ZnII cations with 3-4H and succinic acid produced the generation of dimeric M6-cages where two trinuclear [Zn3-3]2+ cationic clusters were bound by two succinic carboxylate units. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

[Display omitted] Regioselective synthesis of 1,4-difluoro-2,5-dimethyl-3,6-bis-(diphenylphosphoryl)benzene from 1,2,4,5-tetraflouro-3,6-dimethylbenzene and preparation of its coordination polymer with Mn2+ have been developed. The structures of the ligand and the complex have been determined by X-ray diffraction. [ABSTRACT FROM AUTHOR]