Exclusive Solvent-Controlled Regioselective Catalytic Synthesis of Potentially Bioactive Imidazolidineiminodithiones: NMR Analysis, Computational Studies and X-ray Crystal Structures.

Herein, we describe the first consistent regiospecific reaction of isothiocyanates with a variety of substituted N-arylcyanothioformamides in a 1:1 molar ratio to generate a series of imidazolidineiminodithiones decorated with a multitude of functional groups on both aromatic rings. The reaction is carried out at room temperature using a 20 mol% catalytic amount of triethylamine with DMF as the solvent to selectively form the mentioned products with exclusive regioselectivity. The methodology features wide substrate scope, no requirement for chromatography, and good to high reaction yields. The products were isolated by simple ether/brine extraction and the structures were verified by multinuclear NMR spectroscopy and high accuracy mass measurements. The first conclusive molecular structure elucidation of the observed regioisomer was established by single-crystal X-ray diffraction analysis. Likewise, the tautomer of the N-arylcyanothioformamide reactant was proven by X-ray diffraction analysis. Density functional theory computations at the B3LYP-D4/def2-TZVP level in implicit DMF solvent were conducted to support the noted regiochemical outcome and proposed mechanism.

Cobalt Hydrogen-Bonded Organic Framework as a Visible Light-Driven Photocatalyst for CO2 Cycloaddition Reaction.

A novel cobalt hydrogen-bonded organic framework (Co-HOF, C24H14CoN4O8) was synthesized from a mixed linker, that is, 2,5-pyridinedicarboxylic acid (PDC) and 2,2'-bipyridyl (BPY) linkers and cobalt ion through a simple, one-pot, low-cost, and scalable solvothermal method. The Co-HOF was fully characterized using several analytical and spectroscopic techniques including single-crystal X-ray diffraction, diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray, and X-ray photoelectron spectroscopy. The Co-HOF exhibits high thermal and chemical stabilities compared to previously reported HOF materials. Moreover, Co-HOF shows excellent photocatalytic activity under visible light irradiation due to its narrow band gap of 2.05 eV. The cycloaddition reaction of CO2 to variable epoxides was investigated to evaluate the photocatalytic performance of Co-HOF under visible light radiation and was found to produce the corresponding cyclic carbonates in yields up to 99.9%.

First X-ray Crystal Structure Characterization, Computational Studies, and Improved Synthetic Route to the Bioactive 5-Arylimino-1,3,4-thiadiazole Derivatives.

N-arylcyanothioformamides are useful coupling components for building key chemical intermediates and biologically active molecules in an expedited and efficient manner. Similarly, substituted (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides have been utilized in numerous one-step heteroannulation reactions to assemble the structural core of several different types of heterocyclic compounds. Herein, we demonstrate the effectiveness of the reaction of N-arylcyanothioformamides with various substituted (Z)-2-oxo-N-phenylpropanehydrazonoyl chlorides to produce, stereoselectively and regioselectively, a range of 5-arylimino-1,3,4-thiadiazole derivatives decorated with a multitude of functional groups on both aromatic rings. The synthetic methodology features mild room-temperature conditions, large substrate scope, wide array of functional groups on both reactants, and good to high reaction yields. The products were isolated by gravity filtration in all cases and structures were confirmed by multinuclear NMR spectroscopy and high accuracy mass spectral analysis. Proof of molecular structure of the isolated 5-arylimino-1,3,4-thiadiazole regioisomer was obtained for the first time by single-crystal X-ray diffraction analysis. Crystal-structure determination was carried out on (Z)-1-(5-((3-fluorophenyl)imino)-4-(4-iodophenyl)-4,5-dihydro-1,3,4-thiadiazol-2-yl)ethan-1-one and (Z)-1-(4-phenyl-5-(p-tolylimino)-4,5-dihydro-1,3,4-thiadiazol-2-yl)ethan-1-one. Similarly, the tautomeric structures of the N-arylcyanothioformamides and (Z)-geometries of the 2-oxo-N-phenylpropanehydrazonoyl chloride coupling partners were proven by X-ray diffraction studies. As representative examples, crystal-structure determination was carried out on (4-ethoxyphenyl)carbamothioyl cyanide and (Z)-N-(2,3-difluorophenyl)-2-oxopropanehydrazonoyl chloride. Density functional theory calculations at the B3LYP-D4/def2-TZVP level were carried out to rationalize the observed experimental findings.

Toward Confined Carbyne with Tailored Properties.

Confining carbyne to a space that allows for stability and controlled reactivity is a very appealing approach to have access to materials with tunable optical and electronic properties without rival. Here, we show how controlling the diameter of single-walled carbon nanotubes opens the possibility to grow a confined carbyne with a defined and tunable band gap. The metallicity of the tubes has a minimal influence on the formation of the carbyne, whereas the diameter plays a major role in the growth. It has been found that the properties of confined carbyne can be tailored independently from its length and how these are mostly determined by its interaction with the carbon nanotube. Molecular dynamics simulations have been performed to interpret these findings. Furthermore, the choice of a single-walled carbon nanotube host has been proven crucial even to synthesize an enriched carbyne with the smallest energy gap currently reported and with remarkable homogeneity.

Titanium metal-organic frameworks for photocatalytic CO2 conversion through a cycloaddition reaction.

The elevated levels of CO2 in the atmosphere have been a major concern for environmental scientists. Capturing CO2 gas and its subsequent conversion to useful organic compounds is one of the avenues that have been extensively studied in the last decade. The photocatalytic cycloaddition of CO2 is a promising approach for effective CO2 capture and the production of value-added chemicals such as cyclic carbonates. MOF-901, a titanium-based metal-organic framework with hexagonal layers and imine linkages, was successfully oxidized in this study to MOF-997, incorporating amide linkages using Oxone. Both MOFs displayed remarkable photocatalytic activity in CO2 cycloaddition under mild conditions, including moderate temperatures and visible light exposure. Particularly noteworthy is MOF-997, exhibiting superior performance with donor-acceptor active sites, achieving a 99.9% yield in catalyzing CO2 conversion from styrene epoxide to styrene carbonate under solvent conditions.

The isolation of single MMX chains from solution: unravelling the assembly-disassembly process.

Herein, we provide a systematic theoretical and experimental study of the structural and optical properties of MMX (M=metal, X=halide) chains. The influence of solvent, temperature, and concentration has been analyzed to find suitable parameters for initial building-block associations in solution. By using density functional calculations, we have computed the dissociation energy of different MMX oligomers (up to the tetramer) in the gas phase. On the basis of these findings, we discuss the most likely disassembly scenario and propose a new interpretation of these compounds. We also calculated the charge redistribution that occurs upon MM+XMMX binding in vacuum. Time-dependent density functional theory (TDDFT) is used to calculate the UV/visible spectra of different MMX chains up to the tetramer in the gas phase. The implications of these theoretical findings in the analysis of our experiments are discussed in the text. The overall body of data presented suggests a new way of looking at such linear structures. By taking into account these new data, we have been able to isolate single/few MMX chains on mica.

Lanthanide(III) (Er/Ho) coordination polymers for a photocatalytic CO2 cycloaddition reaction.

Two new isostructural carboxylate-bridged lanthanide ribbons having the chemical formula [Ln2(4-ABA)6]n [4-ABA = 4-aminobenzoate, Ln: holmium (Ho) and erbium (Er)] were synthesized by a solvothermal method and fully characterized using multiple analytical, spectroscopic, and computational techniques. Single-crystal X-ray diffraction analysis reveals that both lanthanide coordination polymers (Ln-CPs) exhibit linear ribbon-like structures built up by dinuclear Ln2(4-ABA)6 units and bridged by carboxylate groups. Ln-CPs showed remarkably high thermal and chemical stabilities. Ho-CP and Er-CP exhibited similar band gaps of 3.21 eV and 3.22 eV, respectively, showing their photocatalytic ability under UV light. The photocatalytic activities of Ln-CPs were examined in the CO2 cycloaddition of epoxides to cyclic carbonates under solvent-free conditions, and full conversion (yields up to 99.9%) to the product was achieved. Ln-CP photocatalysts retained the same product yields over five consecutive cycles. Additionally, the experimental magnetic studies indicated that both Ln-CP crystals are antiferromagnetic at low T, which is confirmed by density functional theory calculations.

Author Correction: Polycyclic aromatic chains on metals and insulating layers by repetitive [3+2] cycloadditions.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Polycyclic aromatic chains on metals and insulating layers by repetitive [3+2] cycloadditions.

The vast potential of organic materials for electronic, optoelectronic and spintronic devices entails substantial interest in the fabrication of π-conjugated systems with tailored functionality directly at insulating interfaces. On-surface fabrication of such materials on non-metal surfaces remains to be demonstrated with high yield and selectivity. Here we present the synthesis of polyaromatic chains on metallic substrates, insulating layers, and in the solid state. Scanning probe microscopy shows the formation of azaullazine repeating units on Au(111), Ag(111), and h-BN/Cu(111), stemming from intermolecular homo-coupling via cycloaddition reactions of CN-substituted polycyclic aromatic azomethine ylide (PAMY) intermediates followed by subsequent dehydrogenation. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry demonstrates that the reaction also takes place in the solid state in the absence of any catalyst. Such intermolecular cycloaddition reactions are promising methods for direct synthesis of regioregular polyaromatic polymers on arbitrary insulating surfaces.

Imaging single-molecule reaction intermediates stabilized by surface dissipation and entropy.

Chemical transformations at the interface between solid/liquid or solid/gaseous phases of matter lie at the heart of key industrial-scale manufacturing processes. A comprehensive study of the molecular energetics and conformational dynamics that underlie these transformations is often limited to ensemble-averaging analytical techniques. Here we report the detailed investigation of a surface-catalysed cross-coupling and sequential cyclization cascade of 1,2-bis(2-ethynyl phenyl)ethyne on Ag(100). Using non-contact atomic force microscopy, we imaged the single-bond-resolved chemical structure of transient metastable intermediates. Theoretical simulations indicate that the kinetic stabilization of experimentally observable intermediates is determined not only by the potential-energy landscape, but also by selective energy dissipation to the substrate and entropic changes associated with key transformations along the reaction pathway. The microscopic insights gained here pave the way for the rational design and control of complex organic reactions at the surface of heterogeneous catalysts.