Catalytic Application of Tactically Aligned Cd(II)‐Based Luminescent 3D‐Supramolecular Networks 

Abstract

A new Cd(II) based coordination polymers {[Cd(Azopy)(H2O)4]⋅(NDC)}n (1) has been designed and synthesized by using 4,4′‐Azopyridine (Azopy), and 2, 6‐Naphthalene dicarboxylic acid (NDC) as a linker at ambient condition. The bulk purity of the 1 was analysed by powder X‐ray diffraction (PXRD) analysis, infrared spectroscopy and further confirmed by single crystal X‐ray studies. The crystal structure of 1 revealed a polythreading feature where each 2, 6‐naphthalene dicarboxylate unit are trapped between two one‐dimensional (1D) chain of [Cd(Azopy)(H2O)4]∞ via strong hydrogen bonding interactions. The hydrogen bonding and π⋅⋅⋅π stacking interactions of 1 play a crucial role in the formation of the infinite 3D‐layered supramolecular network. Furthermore, the reduction of nitro‐aromatics to their corresponding amines was performed using green hydrogen source such as D‐glucose in H2O solvent at room temperature. Additionally, the dye adsorption studies revealed that 1 can adsorb Congo Red (CR) dye in a very short span of time. The kinetic study result reveals that the adsorption of CR for 1 is fitted well (R2 =0.996) with a pseudo‐second‐order kinetic model. Moreover, photoluminescence of 1 shows emission in the blue region with λmax at 395 nm and 408 nm at room temperature in the solid state. 1 shows multi‐facet behaviour such as facile synthesis, luminescent nature in solids‐state, emerged as a heterogeneous dye‐adsorbent and catalyst which makes it easy to scaled‐up.

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

“…CP 3 shows vibrations at 3441 cm –1 (νH 2 O), 1583 cm –1 (ν as –COO – ), and 1369 cm –1 (ν as –COO – ) (Figure S19.3). ,,, On the other hand, the FT-IR spectrum of 4 displayed a vibration at 3238 cm –1 which may be attributed to the −N–H stretching band of quaternary amine (CH 3 ) 2 NH 2 + . Furthermore, characteristic ν as and ν s bands of −COO – groups of 2,3-pdca appear at 1633 and 1592 cm –1 and at 1425 and 1382 cm –1 (Figure S19.4), having Δν value >200 cm –1 which indicates that the carboxylates of 2,3-pdca ligand are linked with Cu­(II)/K­(I) adopting bidentate and/or bridged bidentate coordination modes .…”

“…The other important absorption bands that appear in the IR spectrum of 1 are νC−H (2980 cm −1 ) and νCC (1464 cm −1 ) (Figure S19.1). 128 Peaks appearing in the far-IR region indicate the formation of Zn−N and Zn−O bonds. 129 Likewise, 2 exhibited vibration at 3517 cm −1 owing to the coordinated water molecules along with characteristic vibrations associated with ν as and ν s −COO − groups at 1661 and 1555 cm −1 and at 1441 and 1379 cm −1 , respectively (Figure S19.2).…”

Mixed-Ligand Architected Unique Topological Heterometallic Sodium/Cobalt-Based Metal–Organic Framework for High-Performance Supercapacitors

“…In light of the above challenges, herein, we have synthesized a new heterometallic Na/Co-based MOF ( 1 ), [Na 2 Co­(SDCA)­( μ 2 -OH) 2 ( μ 2 -H 2 O) 2 (Azopy)] n , by a facile mixed ligand strategy using 2,5′-thiophenedicarboxylic acid (H 2 SDCA) and 4,4′-azopyridine (Azopy) by slow-diffusion technique at room temperature. It is well-known that multicarboxylate linkers are repeatedly preferred due to their multi coordination manners through the complete/partial deprotonation of −COOH groups in the construction of MOFs. − Here, SDCA is chosen due to its multicoordination ability with metal center through the −COO – group to deliver unique structure with fascinating properties and also its derivatives are widely employed as electrode materials , while the auxiliary pillared Azopy linkers embody the 4-pyridyl building elements, are usually employed as pillars for the extension of frameworks with good flexibility/stability, and the presence of delocalized π-electrons in the pyridyl rings are also accomplished to encourage the electrical conductivity in the resulting MOFs. − Therefore, 1 was expected to give a synergistically enhanced supercapacitor performance with excellent cycling stability, which is also a central idea of the present work.…”