Recent progress in organometallic porphyrin‐based molecular materials for optical sensing, light conversion, and magnetic cooling

Abstract

We present the review of fundamental parameters and properties of metalloporphyrins/phthalocyanines with axial covalent M-O/M-N bonds (M is a metal atom in the oxidation degree more than 2+) for use in the development of the chemistry of molecular materials. The porphyrin complexes covalently bonded along the axial axis are differed by the high oxidation state of a metal atom and related heightened axial reactivity compared with the corresponding derivatives of two charged metal cations, applications of which in both scientific studies and practical areas are most widely reflected in publications. The selection of chemical structures of the 3d, 4d, 5d, and 4f metal derivatives of porphyrins/phthalocyanines and study of their properties promising in the detection of bioactive organic bases, optoelectronics (active components of allsmall molecular organic solar cells), and spintronics (room-temperature magnetocaloric materials) are detailed in the article. The results of the first critical analysis of this topic in the review and the insight into chemical structure effects in the function of MPXs/MPcXs as molecular materials will contribute to further development of their organometallic chemistry.

The p-Metal Porphyrins: from Specificity of Properties to Application in Medicine, Catalysis, and Optoelectronics

“…Because of high affinity to fullerene organic bases, indium(III) porphyrin complexes have good prospects for the development of all-small-molecule organic solar cells (SM-OSCs). [124] Also, they are characterized by the uniquely high molar absorption coefficient at the boundary between the UV and visible regions (B band at the 420 nm, log ε = 4.98 in CHCl 3 , Table 1) that is only slightly different in a solution and solid, the low conduction activation energy (E T = 0.60 eV), and conductivity indifferent to air oxygen (σ vac = 7.1•10 -7 1/Ω cm, σ air = 9.6•10 -8 1/Ω cm). [125] The use of (Cl)InTPP instead of zinc phthalocyanine [126] promises a higher efficiency of photocurrent generation in SM-OSCs.…”

CO2 to CO Electroreduction, Electrocatalytic H2 Evolution, and Catalytic Degradation of Organic Dyes Using a Co(II) meso-Tetraarylporphyrin

“…Inspired by nature that is using metalloporphyrins as antennae molecules, redox shuttles and redox and photo catalysts [ 1 ], researchers have tried to use artificial porphyrin complexes for various purposes in the last decades [ 2 , 3 , 4 , 5 , 6 , 7 , 8 ]. Cobalt porphyrins provide a rich electrochemistry consisting of both metal- (Co(I)/Co(II)/Co(III) and porphyrin-centred redox processes.…”