175444-05-0Relevant academic research and scientific papers
Substituent-Induced Deformed Ni–Porphyrin as an Electrocatalyst for the Electrochemical Conversion of Water into Dioxygen
Krishna, Jonnadula Venkata Suman,Krishna, Narra Vamsi,Singh, Santosh K.,Shaw, Pankaj K.,Dhavale, Vishal M.,Vardhaman, Anil Kumar,Giribabu, Lingamallu
, p. 1549 - 1555 (2018)
The electrochemical water oxidation ability of complexes 5,15-diphenylporphinatonickel(II) (A) and 5,15-bis(3,5-di-tert-butylphenyl)porphinatonickel(II) (B) in the oxygen evolution reaction (OER) have been investigated in an alkaline medium. Complex B was found to be kinetically and thermodynamically more active than complex A. The overpotential and Tafel slope of complex B are lower than those of complex A by 30 mV and around 45 mV/decade, respectively, which supports the higher activity of B. Moreover, stability tests endorse the sustainability of both samples under alkaline conditions. It has been found that the 3,5-di-tert-butylphenyl substituent in B plays a decisive role in achieving a better OER onset potential and current than that obtained with A, which is a result of the modulation of the structural parameters of B. Furthermore, the measured OER activities of A and B have been correlated with their molecular arrangement as well as differences in their bonding characteristics and dipole moments. For further insight, the obtained results have been confirmed by a theoretical study.
Highly Strained, Radially ?-Conjugated Porphyrinylene Nanohoops
Xu, Youzhi,Gs?nger, Sebastian,Minameyer, Martin B.,Imaz, Inhar,Maspoch, Daniel,Shyshov, Oleksandr,Schwer, Fabian,Ribas, Xavi,Drewello, Thomas,Meyer, Bernd,Von Delius, Max
supporting information, p. 18500 - 18507 (2019/11/21)
Small ?-conjugated nanohoops are difficult to prepare, but offer an excellent platform for studying the interplay between strain and optoelectronic properties, and, increasingly, these shape-persistent macrocycles find uses in host-guest chemistry and self-assembly. We report the synthesis of a new family of radially ?-conjugated porphyrinylene/phenylene nanohoops. The strain energy in the smallest nanohoop [2]CPT is approximately 54 kcal mol-1, which results in a narrowed HOMO-LUMO gap and a red shift in the visible part of the absorption spectrum. Because of its high degree of preorganization and a diameter of ca. 13 ?, [2]CPT was found to accommodate C60 with a binding affinity exceeding 108 M-1 despite the fullerene not fully entering the cavity of the host (X-ray crystallography). Moreover, the ?-extended nanohoops [2]CPTN, [3]CPTN, and [3]CPTA (N for 1,4-naphthyl; A for 9,10-anthracenyl) have been prepared using the same strategy, and [2]CPTN has been shown to bind C70 5 times more strongly than [2]CPT. Our failed synthesis of [2]CPTA highlights a limitation of the experimental approach most commonly used to prepare strained nanohoops, because in this particular case the sum of aromatization energies no longer outweighs the buildup of ring strain in the final reaction step (DFT calculations). These results indicate that forcing ring strain onto organic semiconductors is a viable strategy to fundamentally influence both optoelectronic and supramolecular properties.
Silylethynyl substituents as porphyrin protecting groups for solubilization and selectivity control
Oda, Kazuma,Akita, Masanari,Hiroto, Satoru,Shinokubo, Hiroshi
supporting information, p. 1818 - 1821 (2014/04/17)
Silylethynyl substituents are proposed as protecting groups for porphyrin derivatives to enhance their solubility and enable regioselective functionalization. After usage as protecting groups, silylethynyl groups at the meso-positions can be efficiently removed upon heating with aqueous H 2SO4 in the presence of a surfactant. This approach was applied to the preparation of unsymmetrically β-substituted porphyrins and porphin-porphyrin oligomers, which were inaccessible by conventional methods.
Unusual regioselective mercuration of metalloporphyrins and its potential applications
Sugiura, Ken-Ichi,Kato, Aiko,Iwasaki, Kentaro,Miyasaka, Hitoshi,Yamashita, Masahiro,Hino, Shojun,Arnold, Dennis P.
, p. 2046 - 2047 (2008/02/08)
The reaction of Hg(CF3CO2)2 with metalloporphyrins produces mercurated porphyrins regioselectively, the reaction, surprisingly occurring at the most hindered βB-position; this behavior is in marked contrast to the usual electrophilic substitution reactions of porphyrins, whose reactions produce meso-substituted porphyrins; the obtained mercurated porphyrins are active to transition metal-catalyzed coupling reactions, such as the Mizoroki-Heck reaction. The Royal Society of Chemistry.
The Heck reaction for porphyrin functionalisation: Synthesis of meso-alkenyl monoporphyrins and palladium-catalysed formation of unprecedented meso-β ethene-linked diporphyrins
Locos, Oliver B.,Arnold, Dennis P.
, p. 902 - 916 (2007/10/03)
Palladium-catalysed coupling of the vinyl derivatives methyl acrylate, styrene and acrylonitrile with 5-bromo-10,15,20-triphenylporphyrin (MTriPPBr; M = 2H, Ni, Zn) and 5,15-dibromo-10,20-bis(3,5-di-tert-butylphenyl)porphyrin (MDAPBr2) produced
