A Chemically Robust 2D Ni-MOF as an Efficient Heterogeneous Catalyst for One-Pot Synthesis of Therapeutic and Bioactive 2-Amino-3-Cyano-4H-Pyran Derivatives.

Despite possessing numerous catalytic advantages of MOFs, developing 2D frameworks having excellent chemical stability along with new catalytic properties, remains a grand challenge. Herein, by employing a mixed ligand synthetic approach, we have constructed a 2D Ni-MOF, IITKGP-52, which exhibits excellent framework robustness in open air, water, as well as over a wide range of pH solutions (2-12). Benefitting from its robustness and abundant Lewis acidic open metal sites, IITKGP-52 is explored in catalyzing the heterogeneous three-component condensation reaction for the tandem synthesis of bioactive 2-amino-3-cyano-4H-pyran derivatives with low catalytic loading, greater compatibility for a wide range of substrates, excellent recyclability and superior catalytic efficiency than the previously employed homo and heterogeneous systems. IITKGP-52 inaugurates the employment of MOF-based catalysts for one-pot synthesis of therapeutic and bioactive 2-amino-3-cyano-4H-pyran derivatives.

Room-Temperature Superprotonic Conductivity beyond 10-1 S cm-1 in a Co(II) Coordination Polymer.

An efficient design of crystalline solid-state proton conductors (SSPCs) is crucial for the progress of clean energy applications. Developing such materials to make them work at room temperature with a conductivity of ≥10-1 S cm-1 is of significant interest in terms of technical and commercial aspects. Utilizing the recently highlighted "coordinated-water-driven proton conduction" approach, herein, we have rationally synthesized two highly stable and scalable 1D Co(II) coordination polymers (CPs) as SSPCs, PCM-2 {[Co(bpy)(H2O)2(NO3)2]·H2O}n and PCM-3 {[Co2(bpy)2(SO4)2(H2O)6].4H2O}n, with distinct alignments in coordinated water and coordinated oxo-anions (nitrate and sulfate, respectively). The acidity of the metal-bound water molecules in PCM-2 is further enhanced through cooperative long-range continuous H bonds with coordinated Brønsted basic nitrates (proton acceptors), leading to ultrahigh superprotonic conductivities even at 25 °C (1.03 × 10-1 S cm-1 under 95% RH), and reached a maximum of 2.99 × 10-1 S cm-1 at 85 °C (95% RH). The conductivity at 25 °C is even higher than that of commercial Nafion 117 (6.74 × 10-2 S cm-1 at 100% RH). The absence of such an H-bonding interaction in PCM-3 (closed loops) resulted in a lesser conductivity of 5.87 × 10-5 S cm-1 (95% RH, 85 °C). PCM-2 represents the first example of SSPC exhibiting conductivity in the order 10-1 S cm-1 at ambient temperature (25 °C) with excellent recyclability.

A Highly Chemically Robust 3D Interpenetrated MOF Heterogeneous Catalyst for the Synthesis of Hantzsch 1,4-Dihydropyridines and Drug Molecules.

Metal-organic frameworks (MOFs) have attracted immense attention as efficient heterogeneous catalysts over other solid catalysts, however, their chemical environment instability often limits their catalytic potential. Herein, utilizing a flexible unexplored tetra-acid ligand and employing the mixed ligand approach, a 3D interpenetrated robust framework is strategically developed, IITKGP-51 (IITKGP stands for Indian Institute of Technology Kharagpur), which retained its crystallinity over a wide range of pH solution (4-12). Having ample open metal sites (OMSs), IITKGP-51 is explored as a heterogeneous catalyst in one-pot Hantzsch condensation reaction, with low catalyst loading for a broad range of substrates. The synthesis of drug molecules remains one of the most significant and emergent areas of organic and medicinal chemistry. Considering such practical utility, biologically important Nemadipine B and Nifedipine drug molecules (calcium channel protein inhibitor) are synthesized for the first time by using this catalyst and fully characterized via SC-XRD and other spectroscopic methods. This report inaugurates the usage of a MOF material as a catalyst for the synthesis of drug molecules.