Synthesis, Crystal Structure, and Catalytic Properties of Porous 3d‐4f Heterometallic Coordination Polymers Constructed from Pyrazine‐2,3‐dicarboxylic Acid

Abstract

Reactions of pyrazine-2,3-dicarboxylic acid (H 2 pzdc), cobalt nitrate and lanthanide (Ln) oxide under hydrothermal conditions result in four new 3d-4f heterometal coordination polymers, namely, [Ln 2 Co(pzdc) 4 (H 2 O) 6 ]·2H 2 O [Ln = La (1), Pr (2), Eu (3) and Gd (4)]. All compounds were characterized by elemental analysis, infrared spectroscopy, thermal gravimetric analysis, and X-ray diffraction. The compounds exhibit a three-dimensional (3D) brick-like structure with rectangular-shaped nano-scale channels along a axis direction, made up of wave-like layers containing [Ln(pzdc)] + units, which are connected by one-dimensional (1D) chain of [Co(pzdc) 2 ] 2-. The catalytic

Heterometallic coordination polymers: Treatment activity on diabetic foot by reducing the excess inflammatory response in the plantar tissue

“…The structure and design of metallic coordination polymers (CPs) based on crystal engineering are currently of interest in the field of supramolecular chemistry and coordination chemistry. [5][6][7][8] The increasing interest in this field is justified not only by their valuable structures, but also their potential applications in luminescence, catalysis, and biochemistry, and particularly in modern medicinal chemistry. [9][10][11][12][13][14][15] Among the series of compounds fabricated, functional complexes attract great attention due to their potentially valuable drug applications.…”

Toward a Rational Design of 3d-4f Heterometallic Coordination Polymers based on Mixed Valence Copper Centers

“…In recent years, coordination polymers (CPs) have been widely studied in materials science due to their excellent chemical and physical properties, such as porosity, chemical and thermal stability, and catalytic activity, making the rational design of new CPs a continuous challenge for researchers. − In this sense, the combination of two different metal cations in the same structure, such as first row transition (3d) and lanthanide (4f) cations, has been used as a strategy to obtain new CPs with novel structures and potential applications such as magnetic refrigeration, solid state luminescence, and catalysis. − Compared with the lanthanide series, first row transition metals have a richer chemistry as a consequence of the various oxidation states (from +1 to +7) and coordination geometries. Specifically, Cu I and Cu II cations can adopt a wide variety of coordination geometries (linear, trigonal, tetrahedral, trigonal bipyramid, square base pyramid, octahedral) as compared to other transition metal ions.…”

“…15 Thus, Cu II -Ln III heterometallic networks have been reported in the past decade presenting ferromagnetic behavior based on different N,O-bifunctional organic ligands, such as, iminodiacetic acid, 16 glycine, 17 glycinehydroxamic acid, 18 pyrazoledicarboxylic acid 19 and benzotriazolecarboxylic acid. 20 On the other hand, considering that the full shell of Cu I (3d 10 ) can be used as an antenna to improve lanthanide luminescence, Cu I -Ln III emissive materials. 21,22 Literature presents a very rich Cu I -Ln III coordination polymer chemistry in which Cu I is stabilized into extended structures using principally functionalized Nheterocyclic ligands, such as pyridine and pyrazine.…”

Structural Versatility of 3d-CeIII Heterometallic Coordination Polymers Using CoII or CuII

“…On the other hand, using pyrazine-2,3-dicarboxylic acid (H 2 pzdc), Yang et al obtained a series of 3 d -4 f 2D networks [Ln 2 Co­(pzdc) 4 ­(H 2 O) 6 ]·​2H 2 O (Ln = La III , Pr III , Eu III , and Gd III ) that were used as catalysts in the synthesis of cyanohydrin. These compounds showed very high conversions for benzaldehyde and high selectivity to cyanohydrin at room temperature in solvent free conditions . Zhang et al presented an excellent example of multifunctional materials in a family of isostructural 3D compounds [LnZnL­(CO 3 ) 2 ­(H 2 O)] (Ln = Eu III , Gd III , Dy III , Ho III , Er III , Tm III , Yb III , Lu III ; L = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine).…”

“…These compounds showed very high conversions for benzaldehyde and high selectivity to cyanohydrin at room temperature in solvent free conditions. 10 Gd III Zn II framework allowed one to quantify the magnetic interactions between Gd III ions, by the calculation of the coupling constant. 11 The presence of two different metal cations in this type of 3d-4f materials adds structural complexity and gives the possibility of obtaining new functionalities.…”