Preparation, Crystal Structures, and Properties of a Series of Crystalline Tetra(4-sulfonatophenyl)porphyrinato Histidine 4f-3d Porphyrinic Compounds

Abstract

A series of novel 4f-3d crystalline porphyrinic compounds, {[Co(TPPS)] 2 [Ln(Histidine) 5,10,15,20-tetra(4-sulfonatophenyl)porphyrinato) with TPPS and histidine as mixed ligands, have been prepared and characterized by single-crystal X-ray diffraction technique. Complexes 1−3 are isomorphous and characteristic of a threedimensional (3D) framework with the lanthanide ions in two kinds of coordination geometries, i.e., eightfold square antiprism and ninefold monocapped square antiprism. The porphyrin macrocycles adopt a saddle-distorted nonplanar conformation with an embedded cobalt ion binding to four pyrrole nitrogen atoms. As revealed by the photoluminescence measurement, they exhibit blue emission. Variable-temperature magnetic susceptibility reveals that complexes 1−3 are antiferromagnetic. Their FTIR, CV, DPV, and UV/vis results are also studied in detail.

Coordinating Ability of Anions, Solvents, Amino Acids, and Gases towards Alkaline and Alkaline‐Earth Elements, Transition Metals, and Lanthanides

“…For glycinate, six uncoordinated structures were found; of them, two indeed correspond to the amino‐carboxylate anion coordinated to copper atoms, a connectivity that is not disclosed by the CSD, but that was recovered in the category of “semi‐coordinated” structures; the other four correspond to lanthanide‐containing poly‐oxotungstates in which the glycinate ion is coordinated to the lanthanide in a monodentate fashion rather than to the tungsten atoms . Also in the case of histidinate, in the only two structures in which its anion is not coordinated to a nearby transition metal, it is bound to a lanthanide . Finally, the only case of uncoordinated phenylalaninate is found in the presence of a Cd II ion that is wrapped by a tetraazamacrocycle‐based octadentate ligand …”

“…[98] Also in the case of histidinate, in the only two structures in which its anion is not coordinated to an earbyt ransition metal,i ti s bound to al anthanide. [99] Finally,t he only case of uncoordinated phenylalaninate is found in the presence of aC d II iont hat is wrapped by at etraazamacrocycle-based octadentate ligand. [100] As found in the previouss ection for carboxylates, also the amino-carboxylates present varying coordinationa bilities towards transition metals,d epending on their degree of protonation.…”

Porphyrin and phthalocyanine-based metal organic frameworks beyond metal-carboxylates

“…A mixed-ligand MOF is obtained when histidine is added to the reaction mixture. In this case, the amino acid gets coordinated to the Ln ion by its carboxylate part and a new series with chemical formula {[Co(TSPP)]2[Ln(Histidine)-(H2O)][Ln(H3O)3]}n 65 or {[H2(TSPP)]2[Ln(Histidine)-(H2O)][Ln(H3O)3]}n 66,67 are described. In this case, sulfonate coordination modes present more diversity and the asymmetric unit consists of two types of porphyrins and two types of disordered Ln.…”

Preparation, crystal structures, properties, and time-dependent density functional theory of two cobalt complexes with 3-hydroxy-2-methyl-quinoline-4-carboxylate

“…[14][15][16][17][18][19] In this work, all of the complexes are mononuclear complexes with monodentate or bidentate chelated coordination. In continuation of our work, we report here the solvothermal synthesis, X-ray crystal structure, solid-state photoluminescence, solidstate UV-Vis diffuse reflectance and magnetic properties, as well as the time-dependent density functional theory (TDDFT) calculations for three complexes, namely, [ (3). In this paper, complex 3 is the first reported binuclear cobalt complex with HMCA as the main ligand, in which the carboxylate exhibits both monodentate and bidentate chelation.…”

“…In recent years, in the field of chemistry and materials, inorganic–organic hybrid materials have attracted increasing attention from chemists and material scientists, due to their potential applications in semiconductors, 1 optics, 2 magnetism, 3 solar cells, 4 medical materials, 5 and so on.…”