Highly nonplanar, electron deficient, N-substituted tetra-oxocyclohexadienylidene porphyrinogens: structural, computational, and electrochemical investigations

The Journal of Organic Chemistry
Jonathan P HillFrancis D'Souza

Abstract

The structures and electrochemistry of N-benzylated meso-tetrakis (3,5-di-tert-butyl-4-oxo-cyclohexa-2,5-dienylidene) porphyrinogens have been investigated. Structural determinations reveal the isomeric identity of the products obtained from the N-alkylation of the parent meso-tetra (oxo-cyclohexadienylidene) porphyrinogen. The compounds are subject to increased macrocyclic deformations upon increasing N-substitution culminating in the tetra-N-benzyl derivative, which has a buckling superimposed on the already highly puckered macrocycle. The electrochemical analyses emphasize the electron deficiency of the N-benzylated meso-tetra(oxo-cyclohexadienylidene) porphyrinogens and indicate that they can be considered as quinones conjugated via the unsaturated tetrapyrrolic macrocycle. The N-benzylated compounds studied form stable and well-defined pi-cation radical and pi-anion radical species because of their highly conjugated nature. Ab initio molecular orbital calculations at the B3LYP/3-21G() level confirmed the high degree of conjugation between tetrapyrrole and meso substituents and also gave good agreement between calculated and experimentally determined HOMO-LUMO band gap energies.

Citations

Jun 21, 2013·ACS Applied Materials & Interfaces·Shinsuke IshiharaKatsuhiko Ariga
May 31, 2006·Chemical Communications : Chem Comm·Jonathan P HillKatsuhiko Ariga
Sep 24, 2010·Chemical Communications : Chem Comm·Jonathan P HillFrancis D'Souza
Feb 4, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Whitney A WebreFrancis D'Souza
Oct 19, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Mandeep K Chahal, Muniappan Sankar
Oct 20, 2007·Chemistry : a European Journal·Yongshu XieKatsuhiko Ariga
Nov 21, 2007·Angewandte Chemie·Masayuki KaneharaToshiharu Teranishi
Jul 30, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Mandeep K ChahalJonathan P Hill
Jun 23, 2020·Physical Chemistry Chemical Physics : PCCP·Mandeep K ChahalJonathan P Hill
Jul 17, 2020·Chemistry : a European Journal·Mandeep K ChahalJonathan Patrick Hill
Mar 4, 2011·Angewandte Chemie·Shin-ya HayashiAtsuhiro Osuka
Jul 7, 2012·Chemical Communications : Chem Comm·Shunichi FukuzumiJonathan L Sessler
Mar 17, 2012·Chemical Communications : Chem Comm·Shinsuke IshiharaJonathan P Hill
Apr 21, 2018·Chemical Science·Daiki Shimizu, Atsuhiro Osuka
Mar 17, 2012·Chemical Communications : Chem Comm·Jonathan P HillKatsuhiko Ariga
Nov 6, 2009·Journal of the American Chemical Society·Francis D'SouzaShunichi Fukuzumi
Jan 16, 2014·Journal of the American Chemical Society·Jan LabutaJonathan P Hill
Mar 4, 2015·Accounts of Chemical Research·Jan LabutaKatsuhiko Ariga

❮ Previous
Next ❯

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.