Azaindolizine proton cranes attached to 7-hydroxyquinoline and 3-hydroxypyridine: a comparative theoretical study.

Theoretical design of several proton cranes, based on 7-hydroxyquinoline and 3-hydroxypyridine as proton-transfer frames, has been attempted using ground and excited-state density functional theory (DFT) calculations in various environments. Imidazo[1,2-a]pyridine, pyrazolo[1,5-a]pyridine and benzimidazole were considered as proton crane units. The proton crane action requires the existence of a single enol-like form in the ground state, which under excitation goes to the end keto-like one through a series of consecutive excited-state intramolecular proton transfers (ESIPT) and twisting steps with the participation of a crane unit, resulting in a long-range intramolecular proton transfer. The results suggest that 3-hydroxypyridine is not suitable for a proton-transfer frame and 8-(imidazo[1,2-a]pyridin-2-yl)quinolin-7-ol and 8-(pyrazolo[1,5-a]pyridin-2-yl)quinolin-7-ol behave as non-conjugated proton cranes, instead of tautomeric re-arrangement in the latter, which was thought to be possible.

Theoretical Understanding of the Long-Range Proton Transfer Mechanism in 7-Hydroxy Quinoline-Based Molecular Switches: Varma's Proton Crane and Its Analogues.

Herein, the detailed mechanism of intramolecular proton transfer in molecular switches, constructed from 7-hydroxy quinoline substituted in the eight-position C-C single axle, connected to three different proton cranes (morpholine, piperidine, and 1,3,5-dioxazine), was investigated by means of theoretical chemistry. The theoretical interpretation of the rotational mechanism and its stable structures were proposed for the well-known Varma's proton crane, based on morpholine molecule. The reliability of the theoretical simulations was confirmed by the available literature data from time-dependent IR measurements.

Alkynylphosphonium Pt(II) Complexes: Synthesis, Characterization, and Features of Photophysical Properties in Solution and in the Solid State.

A series of heteroleptic bis-alkynyl-diimine mononuclear Pt(II) complexes with alkynylphosphonium and di-tert-butyl-2,2'-bipyridine (dtbpy) ligands have been prepared and characterized by spectroscopic methods and single-crystal XRD. The Pt(II) complexes obtained in the present study demonstrate triplet emission in solution, which originates from 3MLCT/3LC states where the nature of the π-conjugated linker in the alkynylphosphonium ligand manages the contributions of each transition, and this conclusion is supported by DFT calculations. Additionally, the presence of the phosphonium group connected to alkynyl through the π-conjugated linker enhances nonlinear optical properties of the Pt(II) complexes increasing two-photon absorption cross section up to 400 GM. In the solid state, the Pt(II) complexes demonstrate emission that is attributed to 3MMLCT transitions due to the presence of Pt-Pt metallophilic interactions, and the reversible assembly and disassembly of these interactions by grinding and solvent treatment are responsible for the mechanochromic luminescence. It has been experimentally shown that stimuli-responsive emission of the Pt(II) complexes is the result of a "monomer/dimer" transformation; this conclusion is confirmed by DFT calculations for discrete complexes and different dimers with or without Pt-Pt interactions.

Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu4 and Au@Ag4 Clusters Supported by tris(2-Pyridyl)phosphine.

We report herein a family of polynuclear complexes, [Au@Ag4(Py3P)4]X5 and [Au@Cu4(Py3P)4]X5 [X = NO3, ClO4, OTf, BF4, SbF6], containing unprecedented Au-centered Ag4 and Cu4 tetrahedral cores supported by tris(2-pyridyl)phosphine (Py3P) ligands. The [Au@Ag4]5+ clusters are synthesized via controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag4]5+ precursors by the reaction with Au(tht)Cl, while the [Au@Cu4]5+ cluster is assembled through the treatment of a pre-organized [Au(Py3P)4]+ metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M4 clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions. At ambient temperature, the designed compounds emit a modest turquoise-to-yellow luminescence with microsecond lifetimes. Based on the temperature-dependent photophysical experiments and DFT/TD-DFT computations, the emission observed has been assigned to an MLCT or LLCT type depending on composition of the cluster core.

The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes.

In this work we show, using the example of a series of [Cu(Xantphos)(N^N)]+ complexes (N^N being substituted 5-phenyl-bipyridine) with different peripheral N^N ligands, that substituents distant from the main action zone can have a significant effect on the physicochemical properties of the system. By using the C≡C bond on the periphery of the coordination environment, three hybrid molecular systems with -Si(CH3)3, -Au(PR3), and -C2HN3(CH2)C10H7 fragments were produced. The Cu(I) complexes thus obtained demonstrate complicated emission behaviour, which was investigated by spectroscopic, electrochemical, and computational methods in order to understand the mechanism of energy transfer. It was found that the -Si(CH3)3 fragment connected to the peripheral C≡C bond changes luminescence to long-lived intra-ligand phosphorescence, in contrast to MLCT phosphorescence or TADF. The obtained results can be used for the design of new materials based on Cu(I) complexes with controlled optoelectronic properties on the molecular level, as well as for the production of hybrid systems.

Favipiravir-Tautomeric and Complexation Properties in Solution.

The tautomeric properties of favipiravir were investigated experimentally for the first time by using molecular spectroscopy (UV-Vis absorption, fluorescence and NMR), as well as DFT quantum-chemical calculations. According to the obtained results, the enol tautomer is substantially more stable in most of the organic solvents. In the presence of water, a keto form appears to be favored due to the specific solute-solvent interactions. Upon the addition of alkaline-earth-metal ions, deprotonation and complexation occurred simultaneously, giving the formation of 2 : 1 ligand : metal complexes. According to the theoretical simulations, the metal ion is captured between the carbonyl groups as a result of the size-fit effect.

Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene-Terpyridine Subunits.

A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππ stacking, CH-π, and CH-Au, but no aurophilic interactions are realized. The organometallic Au(I) complexes obtained show fluorescence in the solution and dual singlet-triplet emission in the solid state. This means that their photophysical behavior is determined by both intermolecular lattice-defined interactions and Au(I) atom introduction. Density functional theory computational analysis supported the assignment of emission to intraligand electronic transitions only inside the phenylene-terpyridine part with no Au(I) involved. In addition, a study of the nature of the excited states for the "dimer" with an antiparallel orientation of the terpyridine fragment showed that this orientation leads to the generation of abstracted singlet and triplet states, lowering their energy in comparison with the monomer complex. Thus, the complexes obtained can be qualified as examples of Au(I)-containing organometallic aggregation-induced-emission luminogens.

Self-catalytic mechanism of prebiotic reactions: from formamide to pterins and guanine.

Reaction pathway of prebiotic reactions for formation of the pteridines: pterin, xanthopterine, isoxanthopterine and leucopterine, as well as the purine nucleobase guanine from pure formamide are presented. In these reactions, formamide or its tautomer, formimidic acid, play the role of proton-carrying catalyst. All required raw materials, such as hydrogen cyanide, ammonia, water, formic acid, urea, 2-aminomalononitrile, glyoxal, glyoxylic acid and oxalic acid needed in the self-catalyzed reactions are obtained by partial decomposition of formamide. We show that the prebiotic formation of nucleobases and pterins is closely linked and they probably coexisted at the beginning of chemical evolution.

Chemical evolution: from formamide to nucleobases and amino acids without the presence of catalyst.

Abiotic synthesis of nucleobases and amino acids is of critical importance as it sheds light on potential prebiotic chemical reactions. During thermal decomposition of formamide in vacuum conditions, purine, cytosine, adenine, hypoxanthine, uracil, pterin, urea, urocanic acid, glycine, alanine and norvaline were detected. The compounds were obtained without catalyst by heating at 100-180 °C or microwave heating of formamide. Reaction network of self-catalyzed chemical reactions is suggested, showing how from only one parent molecule, nucleobases, urea and the amino acid glycine can be produced. The reaction pathways are theoretically determined using SCS-MP2 calculations.Communicated by Ramaswamy H. Sarma.

Molecular dynamics simulation of carbon dioxide diffusion in NaA zeolite: assessment of surface effects and evaluation of bulk-like properties.

Molecular dynamics simulations were carried out for a finite sample of NaA zeolite in contact with bulk carbon dioxide in a wide range of temperatures and CO2 contents. Density and diffusion profiles were obtained to estimate the depth at which the external surfaces of the zeolite affect CO2 diffusion in porous space. The approximate depth of surface effects for NaA zeolite was estimated as ca. 2 nm, though this figure may vary depending on temperature and adsorbed gas density. Diffusion coefficients and diffusion activation energies were calculated for CO2 and Na+ in the bulk-like region of the zeolite. Diffusion activation energy for carbon dioxide demonstrated a non-monotonic dependence on the amount of adsorbed gas.