Unveiling the Noncovalent Interaction of Thiazol-2-ylidene and Its Derivatives as N-heterocyclic Carbene with Different Proton Donor Molecules

The importance of noncovalent interaction has gained attention in various domains covering drug and novel catalyst design. The present study mainly characterizes the role of hydrogen bond (H-bond) and other intermolecular interactions in different (1 : 1) complex analogues formed between the N-aryl-thiazol-2-ylidene (YR) and five proton donor (HX) molecules. The analysis of the singlet-triplet energy gap ( ) confirmed the stability of the singlet state for this class of N-aryl-thiazol-2-ylidenes than the triplet state. The interaction energy values of the YR-HX complexes follow the order: YR-NH₃<YR-HCN<YR-H₂O<YR-MeOH<YR-HF. In addition, substituting the H-atom of the N−H bond with bulky groups (−R) leads to an increase in the interaction energy of the YR-HX complexes. Hence, it was found that the replacement of N-atom in N-heterocyclic carbene (NHC) by S-atom forming N-aryl-thiazol-2-ylidene results in comparable intermolecular interactions with proton donor molecules similar to imidazole-2-ylidene (NHC). The current study enlightened the role of noncovalent interactions in carbene complexes with proton donor molecules. We hope that our work on carbene chemistry will pave the way for its application in the designing and synthesis of efficient catalysts.     

Copper-Catalyzed Acceptorless Dehydrogenative Coupling of 2-Aminoaryl Methanols with Nitriles for Accessing Quinazolines and Quinolines

A copper acetate monohydrate catalyzed simple, effective and economic protocol has been developed for the construction of quinazoline derivatives via acceptorless dehydrogenative coupling of easily available 2-aminoaryl methanols and nitriles. The methodology was also highly effective for the synthesis of medicinally important quinolines analogues. The reactions proceeded in presence of KO^tBu in toluene at 110 °C for 5 h without the requirement of inert condition, external additives and ligands.     

Nitrogen-Doped TiO2 Nanotubes-Catalyzed Synthesis of Small D-π-A-Type Knoevenagel Adducts and β-Enaminones

For the first time, interstitial nitrogen-doped TiO₂ nanotubes (INDTNTs) have been utilized as heterogeneous green catalysts for the synthesis of D-π-A-type Knoevenagel adducts ( 3 ) and β-enaminones ( 6 ). Notable advantages of the present method include its wide substrate scope, low catalyst loading, avoiding the use of hazardous bases and solvents, products do not require chromatographic purification, high yields, catalyst reusability, etc. The optimized catalyst, INDTNTs-4 has been characterized by XRD, HRTEM, and XPS techniques. The photophysical and electrochemical properties of D-π-A-type 3 and 6 have been evaluated. The study revealed that the colour tunability (cold white light to orange light) and the HOMO/LUMO levels depend mainly on the presence of various electron donating and withdrawing groups on the aromatic/heteroaromatic rings of 3 and 6 . The results indicate that the D-π-A-type 3 and 6 could be promising materials for the fabrication of optoelectronic devices.     

A Luminescent Zinc(II) Coordination Polymer for Selective Detection of Fe3+ and Cr2O72− in Water and Catalytic CO2 Fixation

Fluorescence-based detection technique using coordination polymer has been considered an attractive alternative over conventional approaches. Herein, a new luminescent zinc(II) coordination polymer, [Zn(4-ABPT)(NIPA)(H₂O)], SSICG-5 , is synthesized by using a Lewis acidic Zn(II) ion, aromatic nitro group containing ligand 5-nitroisophthalic acid (H₂NIPA), and basic −NH₂ rich ligand 3,5-di(pyridine-4-yl)-4H-1,2,4-triazol-4-amine (4-ABPT). SSICG-5 can detect Fe³⁺ and Cr₂O₇²⁻ selectively with a LOD of 0.16 μM and 1.94 μM, respectively. Additionally, carbon dioxide (CO₂) fixation via one-pot CO₂ cycloaddition reaction has significant importance for reduced waste formation, minimizing reaction time and lowering chemical usage. Zn metal centre of SSICG-5 possesses a replaceable coordinated water molecule. The active metal sites combined with the Lewis acidic and basic sites of the ligands make SSICG-5 an ideal bifunctional heterogeneous catalyst for efficient CO₂ cycloaddition reaction under room temperature (RT), solvent-free conditions. Notably, SSICG-5 exhibits near quantitative conversion (turnover number (TON) of 198) of propylene oxide to its carbonate compound under mild reaction conditions.