Series of Porous 3-D Coordination Polymers Based on Iron(III) and Porphyrin Derivatives

Abstract

A new series of 3-D coordination polymers based on iron(III) and nickel(II) tetracarboxylate porphyrin (Ni-TCPP) have been produced using solvothermal conditions. MIL-141(A) solids (MIL stands for Material from Institut Lavoisier), formulated Fe(Ni-TCPP)A•(DMF) x (A = Li, Na, K, Rb, Cs, DMF = N,N-dimethylformamide, x ∼ 3), are built up from three anionic interpenetrated PtS-type networks charge-balanced by alkali cations (A) entrapped inside the pores. MIL-141(A) thus includes three types of cations, two of which may act as coordinatively unsaturated metal sites (Ni2+ and A+). These solids all present a permanent porosity with a reasonably high surface area (SBET = 510–860 m2 g–1) as well as some structural flexibility toward adsorption/desorption processes, modulated in both cases by the nature of A. Thermally Stimulated Current (TSC) measurements indicated that alkali cations are rather homogeneously distributed within the pores, while their interaction with the framework is stronger in MIL-141(A) than in the analogous cation-containing Faujasites X and Y zeolites. Finally, high pressure adsorption isotherms of N2 and O2 were measured. Whereas alkali ion-containing zeolites adsorb selectively N2 toward O2, the opposite is observed for MIL-141(A). This result is interpreted in light of the TSC data and the possible preferential interaction of the porphyrinic linker with O2.

Porphyrin polymers and organic frameworks

“…Single-crystal X-ray crystallography showed each porphine linked to eight indium clusters, creating a novel close-packed cage structure. The net charge on the cages 67 can be adjusted by the degree of metallation. The MOFs are effective catalysts for photo-oxidation of sulfides to sulfoxides in the presence of O 2 .…”

“…Newly reported porphyrin MOF/COF coordination polymer systems for optoelectronic applications also continue to grow. 67,68 Using porous porphyrin polymer materials for catalytic applications is highly attractive due to their large surface area, strong light absorption and the potential for simultaneous product formation and storage. Several recent reports have shown promise for these materials to act as both light harvesters and catalysts for a variety of reactions including solar fuel-forming reactions such as water photoelectrolysis.…”

“…Surface areas were as high as 860 m 2 g −1 , and the MOFs in general showed an adsorption selectivity favoring O 2 over N 2 . 67 Fateeva et al synthesized a water-stable MOF using TCPP and [AlOH] 2 by reacting AlCl 3 ·6H 2 O with free-base TCPP under hydrothermal conditions (Fig. 28).…”

Biomimicry in metal–organic materials

“…The most notable problem is that metalloporphyrins are susceptible to dimerization via oxo-bridging interactions, which terminates its catalytic activity via blocking of the active site [220]. In order to solve this problem and construct metalloporphyrin-incorporated artificial enzymes, several distinctive strategies were developed: (1) encapsulation of porphyrins into the cavities of porous materials (silica [234], surface modified silica [235,236], synthetic molecular sieves [237], clays [238], layered metal oxide semiconductors (LMOS) [239], zeolites [240], diamond nano-particles [241], and MOFs [242][243][244][245][246]), (2) immobilization of the porphyrin into the struts of a framework (hydrogen bond network solids [247] and MOFs [248][249][250][251][252][253][254][255][256][257][258][259][260][261][262][263][264][265]), and (3) appending the porphyrin onto a surface (Fullerenes [266,267] and nanotubes [268,269]).…”

“…The artificial synthesis of porphyrins [276] has inspired scientists to synthesize MOF structural ligands with both a porphyrin center and coordinating moieties (carboxylic acids, pyridines, etc.). Currently, a variety of metalloporphyrin-incorporated MOFs have been synthesized [248][249][250][251][252][253][254][255][256][257][258][259][260][261][262][263][264][265]. Their ligands, catalytic / biomimetic activities and the corresponding references are summarized in Table 1.…”