Heteroleptic Zn(II)–Pentaiodobenzoate Complexes: Structures and Features of Halogen–Halogen Non-Covalent Interactions in Solid State

Reactions between Zn(II) nitrate, pentaiodobenzoic acid (HPIBA) and different pyridines in dimethylformamide (DMF) result in the formation of the heteroleptic neutral complexes [Zn(3,5-MePy)2PIBA2] (1) and [Zn(DMF)3(NO3)PIBA] (2). Both compounds were isolated in pure form, as shown by the PXRD data. The features of specific non-covalent interactions involving halogen atoms (halogen bonding) were examined by means of DFT calculations (QTAIM analysis and the estimation of corresponding energies)

Heteroleptic Zn(II)–Pentaiodobenzoate Complexes: Structures and Features of Halogen–Halogen Non-Covalent Interactions in Solid State

Reactions between Zn(II) nitrate, pentaiodobenzoic acid (HPIBA) and different pyridines in dimethylformamide (DMF) result in the formation of the heteroleptic neutral complexes [Zn(3,5-MePy)2PIBA2] (1) and [Zn(DMF)3(NO3)PIBA] (2). Both compounds were isolated in pure form, as shown by the PXRD data. The features of specific non-covalent interactions involving halogen atoms (halogen bonding) were examined by means of DFT calculations (QTAIM analysis and the estimation of corresponding energies)

Supramolecular Diiodine-Bromostannate(IV) Complexes: Narrow Bandgap Semiconductors

Three supramolecular bromostannates(IV) with “trapped” diiodine molecules, Cat2{[SnBr6](I2)} (Cat = Me4N+ (1), 1-MePy+ (2) and 4-MePyH (3)), were synthesized. In all cases, I2 linkers are connected with bromide ligands via halogen···halogen non-covalent interactions. Articles 1–3 were studied using Raman spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy. The latter indicates that 1–3 are narrow band gap semiconductors

Organometallic derivatives of Rh- and Ir-substituted polyoxotungstates with Keggin structure: reactivity screening by electrospray ionization mass-spectrometry

ESI-MS based methodology for the rapid reactivity screening of [PW11O39RhCl]5− and [PW11O39Ir(H2O)]4− toward various metalation-intended substrates (reagents with an activated C–H bond, boronic acids and organotin compounds) is presented. Formation of a series of new organometallic POM derivatives with Rh–R (R = malonate, phenylacetate, CH3, Ph, ferrocenyl) and Ir–R (R = CH3) bonds is reported

Selenium(IV) Polybromide Complexes: Structural Diversity Driven by Halogen and Chalcogen Bonding

Reactions between bromoselenate(IV)-containing solutions, dibromine and salts of pyridinium-family organic cations resulted in structurally diverse, bromine-rich polybromine-bromoselenates(IV): (4-MePyH)5[Se2Br9][SeBr6](Br3)2 (1), (2-MePyH)2{[SeBr6](Br2)} (2), (PyH)2{[SeBr5]Br(Br2)2} (3), (1-MePy)2{[SeBr6](Br2)} (4). The compounds feature halogen and (in the case of 3) chalcogen bonding in solid state, resulting in formation of supramolecular architectures of different dimensionality. DFT calculations allowed estimation of the energies of non-covalent interactions in 1–4; additionally, characterization by Raman spectroscopy was performed

Trimethylammonium Sn(IV) and Pb(IV) Chlorometalate Complexes with Incorporated Dichlorine

Supramolecular dichloro-chlorostannate(IV) and -plumbate(IV) complexes (Me3NH)2{[MCl6]Cl2} (M = Sn (1), Pb (2)) feature dichlorine units incorporated into a halometalate framework. Both compounds were characterized by X-ray diffractometry and Raman spectroscopy

Peek Inside the Water Mixtures of Ionic Liquids at Molecular Level: Microscopic Properties Probed by EPR Spectroscopy

Many ionic liquids (ILs) can be mixed with water, forming either true solutions or emulsions. This favors their applications in many respects, but at the same time might strongly alter their physicochemical properties. A number of methods exist for studying the macroscopic properties of such mixtures, whereas understanding their characteristics at micro/nanoscale is rather challenging. In this work we investigate microscopic properties, such as viscosity and local structuring, in binary water mixtures of IL [Bmim]BF4 in liquid and glassy states. For this sake, we use continuous wave and pulse electron paramagnetic resonance (EPR) spectroscopy with dedicated spin probes, located preferably in IL-rich domains or distributed in IL- and water-rich domains. We demonstrate that the glassy-state nanostructuring of IL-rich domains is very similar to that in neat ILs. At the same time, in liquid state the residual water makes local viscosity in IL-rich domains noticeably different compared to neat ILs, even though the overwhelming amount of water is contained in water-rich domains. These results have to be taken into account in various applications of IL-water mixtures, especially in those cases demanding the combinations of optimum micro- and macroscopic characteristics

Complexes of M3S44+ (M = Mo, W) with chiral alpha-hydroxy and aminoacids: Synthesis, structure and solution studies

New complexes of triangular clusters M3S4 4+ (M = Mo, W) with incomplete cuboidal metal–chalcogenide framework bearing chiral a-hydroxy and amino acids have been prepared. L-lactic acid (H2lac), L-mandelic acid (H2man), and L-alanine (Hala) react with [W3S4Br4(PPh3)3] in 1:1 ratio to yield, respectively, monosubstituted complexes [W3S4(PPh3)3Br3(Hlac)(CH3CN)] (1), [W3S4(PPh3)3Br3(Hman)(CH3CN)] (2), and [W3S4(PPh3)3Br3(Hala)(CH3CN)]Br (3). In the presence of base [Mo3S4Cl4(PPh3)3] gives trisubstituted complexes [Mo3S4(PPh3)3(Hlac)2(lac)] (4) and [Mo3S4(PPh3)3(Hman)3]Cl (5). Circular dichroism studies of 4 indicate chirality transfer from the ligand to the Mo3S4 4+ cluster core. These complexes incorporate Cu+ with the formation of corresponding {M3CuS4}5+ cuboidal derivatives. NMR and ESI-MS studies of solution behavior are presented

Active Pharmaceutical Ingredient-Ionic Liquids (API-ILs): Nanostructure of the Glassy State Studied by Electron Paramagnetic Resonance Spectroscopy

Active Pharmaceutical Ingredient-Ionic Liquids (API-ILs) draw increasing interest as a particular class of ILs that possess unusual physicochemical properties along with simultaneous potentials for pharmaceutical applications. Although nanostructuring phenomena were actively investigated in common ILs, their studies in API-ILs are scarce so far. In this work, using the complex methodology of Electron Paramagnetic Resonance (EPR) and dissolved spin probes, we investigate nanostructuring phenomena in a series of API-ILs: [Cnmim][Ibu], [Cnmim][Gly], and [Cnmim][Sal] with n = 2, 4, and 6, respectively. We reveal similar trends for API-ILs and common ILs, as well as peculiarities inherent to the studied API-ILs. Unusual behavior observed for [Cnmim][Ibu] has been assigned to the presence of a non-polar fragment in the [Ibu]− anion, which leads to the formation of more complex nanostructures around the radical compared to common ILs. Understanding general trends in the formation of such self-organized molecular structures is of fundamental interest and importance for applying API-ILs

Two-Dimensional and Three-Dimensional Coordination Polymers Based on Ln(III) and 2,5-Diiodoterephthalates: Structures and Luminescent Behavior

Five new coordination polymers based on Ln3+ and 2,5-diiodoterephthalates (2,5-I-bdc)— {[La2(2,5-I-bdc)3(DMF)4]}·2DMF (1) and {[Ln2(2,5-I-bdc)3(DMF)4]} (Ln = La (2), Nd (3), Sm (4) and Eu (5))—were prepared and characterized by single crystal and powder X-ray diffractometry. Luminescent behavior was examined (the highest quantum yield is 4.5%); thermal stability was examined using thermogravimetric analysis