American Chemical Society
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Catalytic C–H Bond Activation and Knoevenagel Condensation Using Pyridine-2,3-Dicarboxylate-Based Metal–Organic Frameworks

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journal contribution
posted on 2021-05-12, 18:05 authored by Rampal Pandey, Durgesh Singh, Neha Thakur, Krishna K. Raj
Three 1D coordination polymers (CPs) [M­(pdca)­(H2O)2]n (M = Zn, Cd, and Co; 1–3), and a 3D coordination framework {[(CH3)2NH2]­[CuK­(2,3-pdca)­(pa)­(NO3)2]}n (4) (2,3-pdca = pyridine-2,3-dicarboxylate and pa = picolinic acid), have been synthesized adopting a solvothermal reaction strategy. The CPs have been thoroughly characterized using various spectral techniques, that is, elemental analyses, FT-IR, TGA, DSC, UV/vis, and luminescence. Structural information on 1–4 was obtained by PXRD and X-ray single-crystal analyses, whereas morphological insights were attained through FESEM, AFM, EDX, HRTEM, and BET surface area analyses. Roughness parameters were calculated from AFM analysis, whereas dimensions of small domains and interplanar spacing were defined with the aid of HRTEM. CPs 1–3 are 1D isostructural networks, whereas 4 is a 3D framework. Moreover, 1–4 display moderate luminescence at rt. In addition, 1–4 have been applied as economic and efficient porous catalysts for the Knoevenagel condensation reaction and C–H bond activation under mild conditions with good yields (95–98 and 97–99%), respectively. Notably, 1–3 can be reused up to seven cycles, whereas 4 can be reused up to five catalytic cycles with retained catalytic efficiency. Relative catalytic efficacy toward the Knoevenagel condensation reaction follows in the order 2 > 1 > 3 > 4, whereas 2 > 4 > 1 > 3 for C–H activation. The present result demonstrates synthetic, structural, optical, morphological, and catalytic aspects of 1–4.