A review on oxime functionality: an ordinary functional group with significant impacts in supramolecular chemistry.

The oxime functional group is pivotal in chemistry, finding extensive applications in medical science, catalysis, organic functional group transformations, and the recognition of essential and toxic analytes. While the coordination chemistry of oxime derivatives has been thoroughly explored and several reviews have been published on this topic in reputable journals, a comprehensive review encompassing various aspects such as crystal engineering, cation and anion recognition, as well as coordination chemistry activities, is still in demand. This feature article highlights the diverse applications of oxime derivatives across multiple domains of chemistry, including medicine, agriculture, crystal engineering, coordination chemistry, and molecular recognition studies. Each of the oxime derivatives in this feature article are meticulously described in terms of their medicinal applications, crop protection, crystal engineering attributes, analyte recognition capabilities, and coordination chemistry aspects. By providing a comprehensive overview of their versatile applications, this article aims to inspire researchers to explore and develop novel oxime-based derivatives for future applications.

C-H Bond Activation by an Antimony(V) Oxo Intermediate Accessed through Electrochemical Oxidation of Antimony(III) Tetrakis(thiocyano)corrole.

A new class of antimony(III) corroles has been described. The photophysical properties of these newly synthesized tetrakis(thiocyano)corrolatoantimony(III) derivatives having four SCN groups on the bipyrrole unit of corrole are drastically altered compared to their ß-unsubstituted corrolatoantimony(III) analogues. The UV-vis and emission spectra of tetrakis(thiocyano)corrolatoantimony(III) derivatives are significantly red-shifted (roughly 30-40 nm) in comparison with their ß-unsubstituted corrolatoantimony(III) derivatives. The Q bands are significantly strengthened. The intensity of the most prominent Q band is roughly 70% that of the Soret band and absorbs strongly at the far-red region, i.e., at 700-720 nm. These molecules emit light in the near-infrared region (700-900 nm). Tetrakis(thiocyano)corrolatoantimony(III) undergoes electrochemical anodic oxidation to form SbV═O species, which facilitates electrocatalytic oxygen evolution reaction (OER) and the activation of benzylic C-H to produce benzoic acid selectively. Under optimized conditions, SbIII-corrole@NF (NF = nickel foam) required an overpotential of 380 mV to reach a 50 mA cm-2 current density, comparable with those of other transition-metal-based complexes. On the other hand, replacing the anodic OER with benzyl alcohol oxidation lowered the required potential by 150 mV (at 300 mA cm-2) to improve the energy efficiency of the electrochemical process.

Free-Base Corrole Anion.

Free-base corroles have long been known to be acidic, readily undergoing deprotonation by mild bases and in polar solvents. The conjugate base, however, has not been structurally characterized until now. Presented here is a first crystal structure of a free-base corrole anion, derived from tris(p-cyanophenyl)corrole, as the tetrabuylammonium salt. The low-temperature (100 K) structure reveals localized hydrogens on a pair of opposite pyrrole nitrogens. DFT calculations identify such a structure as the global minimum but also point to two cis tautomers only 4-7 kcal/mol above the ground state. In terms of free energy, however, the cis tautomers are above or essentially flush with the trans-to-cis barrier so the cis tautomers are unlikely to exist or be observed as true intermediates. Thus, the hydrogen bond within each dipyrrin unit on either side of the molecular pseudo-C2 axis through C10 (i.e., between pyrrole rings A and B or between C and D) qualifies as or closely approaches a low-barrier hydrogen bond. Proton migration across the pseudo-C2 axis entails much higher activation energies >20 kcal/mol, reflecting the relative rigidity of the molecule along the C1-C19 pyrrole-pyrrole linkage.

ICT and AIE Characteristics Two Cyano-Functionalized Probes and Their Photophysical Properties, DFT Calculations, Cytotoxicity, and Cell Imaging Applications.

Two probes, AIE-1 and AIE-2, were synthesized to investigate the effect of substitutional functional group on aggregation (aggregation-caused quenching (ACQ) or aggregation-induced emission (AIE)) and intramolecular charge transfer (ICT) behavior as well as on the cell imaging aspect. The yellow-color non-substituted probe AIE-1 showed weak charge-transfer absorption and an emission band at 377 nm and 432 nm, whereas the yellowish-orange color substituted probe AIE-2 showed a strong charge-transfer absorption and an emission band at 424 nm and 477 nm in THF solvent. The UV-Vis studies of AIE-1 and AIE-2 in THF and THF with different water fractions showed huge absorption changes in AIE-2 with high water fractions due to its strong aggregation behavior, but no such noticeable absorption changes were observed for AIE-1. Interestingly, the fluorescence intensity of AIE-1 at 432 nm gradually decreased with increasing water fractions and became almost non-emissive at 90% water. However, the monomer-type emission of AIE-2 at 477 nm was shifted to 584 nm with a 6-fold increase in fluorescence intensity in THF-H2O (1:9, v/v) solvent mixtures due to the restriction of intramolecular rotation on aggregation in high water fractions. This result indicates that the probe AIE-1 shows ACQ and probe AIE-2 shows AIE behaviors in THF-H2O solvent mixtures. Furthermore, the emission spectra of AIE-1 and AIE-2 were carried out in different solvent and with different concentrations to see the solvent- or concentration-dependent aggregation behavior. Scanning electron microscope (SEM) and dynamic light scattering (DLS) experiments were also conducted to assess the morphology and particle size of two probes before and after aggregation. Both of the probes, AIE-1 and AIE-2, showed less toxicity on HeLa cells and were suitable for cell imaging studies. Density functional theory (DFT) calculation was also carried out to confirm the ICT process from an electron-rich indole moiety to an electron-deficient cyano-phenyl ring of AIE-1 or AIE-2.

Copper(II), Zinc(II), and Cadmium(II) Formylbenzoate Complexes: Reactivity and Emission Properties.

Synthesis, characterization, reactivity, and sensing properties of 4-formylbenzoate complexes of copper(II), zinc(II), and cadmium(II) possessing the 1,10-phenanthroline ancillary ligand are studied. The crystal structures of the (1,10-phenanthroline)bis(4-formylbenzoate)(aqua)copper(II) and (1,10-phenanthroline)bis(4-formylbenzo-ate)zinc(II) and a novel molecular complex comprising an assembly of mononuclear and dinuclear species of (1,10-phenanthroline)bis(4-formylbenzoate)cadmium(II) are reported. These zinc and cadmium complexes are fluorescent; they show differentiable sensitivity to detect three positional isomers of nitroaniline. The mechanism of sensing of nitroanilines by 1,10-phenanthroline and the complexes are studied by fluorescence titrations, photoluminescence decay, and dynamic light scattering. A plausible mechanism showing that 1,10-phenanthroline ligand-based emission quenched by electron transfer from the excited state of 1,10-phenanthroline to nitroaniline is supported by density functional theory calculations. In an anticipation to generate a fluorescent d10-copper(I) formylbenzoate complex by a mild reducing agent such as hydroxylamine hydrochloride for similar sensing of nitroaromatics as that of the d10-zinc and cadmium 4-formylbenzoate complexes, reactivity of d9-copper(II) with hydroxylamine hydrochloride in the presence of 4-formylbenzoic acid and 1,10-phenanthroline is studied. It did not provide the expected copper(I) complex but resulted in stoichiometry-dependent reactions of 4-formylbenzoic acid with hydroxylamine hydrochloride in the presence of copper(II) acetate and 1,10-phenanthroline. Depending on the stoichiometry of reactants, an inclusion complex of bis(1,10-phenanthroline)(chloro)copper(II) chloride with in situ-formed 4-((hydroxyimino)methyl)benzoic acid or copper(II) 4-(hydroxycarbamoyl)benzoate complex was formed. The self-assembly of the inclusion complex has the bis(1,10-phenanthroline)(chloro)copper(II) cation encapsulated in hydrogen-bonded chloride-hydrate assembly with 4-((hydroxyimino)methyl)benzoic acid.

Four-coordinated see-saw N-(aryl)-2-(propan-2-ylidene)hydrazinecarbothioamide complexes of nickel(ii), copper(ii) and zinc(ii) and their propensity for catalytic cyclisation.

A series of mononuclear complexes of divalent nickel and zinc with N-(4-methoxyphenyl)-2-(propan-2-ylidene)hydrazine carbothioamide (H2Lmethoxy) as well as with N-(4-nitrophenyl)-2-(propan-2-ylidene)hydrazine carbothioamide (H2Lnitro) have been structurally characterised. Among these two ligands, H2Lnitro formed an analogous copper(ii) complex to that of nickel and zinc, whereas H2Lmethoxy undergoes a catalytic cyclisation reaction in the presence of copper(ii) nitrate trihydrate. Control experiments based on ESR have revealed that copper(ii) is reduced to copper(i) and reverts back to copper(ii) as the cyclisation reaction proceeds, generating a catalytic reaction. The crystal structures of H2Lnitro and H2Lmethoxy show that the plane of the phenyl ring with respect to the plane of the hydrazine-containing unit in H2Lnitro is more or less coplanar, whereas the H2Lmethoxy molecule is non-planar with a 67.05° angle between these planes. DFT calculations have shown a large difference in the localisation of electrons in the HOMO of the two ligands; the HOMO of H2Lmethoxy is spread over the aromatic ring, which facilitates involvement of the ring in the formation of a C-N bond through a single electron transfer to a copper(ii) ion. This cyclic product has a distinguishable absorption maximum at 299 nm, which makes it possible to detect copper ions over other first row transition metal ions and alkali metal ions. On the other hand, the copper(ii) complex of H2Lnitro shows a characteristic absorption at 395 nm in the presence of fluoride ions, whereas the free ligand with fluoride shows absorption at 418 nm, which shows that the interactions of the ligand with fluoride and with the corresponding copper complex widely differ.

Conformation and Visual Distinction between Urea and Thiourea Derivatives by an Acetate Ion and a Hexafluorosilicate Cocrystal of the Urea Derivative in the Detection of Water in Dimethylsulfoxide.

Structures of different solvates and solute-solvent interactions of 4-(3-(4-nitrophenyl)urido)benzoate (L 1 ) and methyl-4-(3-(4-nitrophenyl)thiourido)benzoate (L 2 ) with different solvents are analyzed. The solution of L 1 with tetrabutylammonium acetate (TBAA) in dimethylsulfoxide (DMSO) is colorless, but a similar solution of L 2 with TBAA is orange. On the other hand, respective solutions of these urea and thiourea derivatives with tetrabutylammonium fluoride (TBAF) in DMSO are orange. Urea derivative L 1 facilitates the reaction of TBAF with glass to form tetrabutylammonium hexafluorosilicate, which on further interaction with L 1 forms cocrystal 2L 1 ·(TBA)2SiF6. Reorganization of hydrogen-bonded self-assembly of 2L 1 ·(TBA)2SiF6 in DMSO caused by water is established by a dynamic light scattering study. With an increase in the amount of water in the solution, visual color changes from orange to colorless, and the color changes are reversed upon the addition of a dehydrating agent such as molecular sieves. Solvates of L 1 with DMSO, dimethylformamide (DMF), and dimethylacetamide are quasi-isostructural. The respective self-assembly of these solvates differs due to orientations of aromatic rings and the carbomethoxy group across the thioamide/amide bond. Significant differences in self-assemblies of the respective DMSO solvate of L 1 and L 2 are observed; self-assembly of the former has dimeric subassemblies as repeat units, whereas the latter has monomeric subassemblies. DMF solvates of L 1 and dimethylacetamide of L 1 are built by dimeric subassemblies to form self-assembled structures, but these subassemblies differ in the orientation of the carbomethoxy group across the urea units.