Fully π-Conjugated Helices from Oxidative Cleavage of <i>meso</i>-Aryl-Substituted Expanded Porphyrins

Fully π-Conjugated Helices from Oxidative Cleavage of meso-Aryl-Substituted Expanded Porphyrin

Fully π-Conjugated Helices from Oxidative Cleavage of <i>meso</i>-Aryl-Substituted Expanded Porphyrins

Fully π-Conjugated Helices from Oxidative Cleavage of meso-Aryl-Substituted Expanded Porphyrin

Fully π-Conjugated Helices from Oxidative Cleavage of <i>meso</i>-Aryl-Substituted Expanded Porphyrins

Fully π-Conjugated Helices from Oxidative Cleavage of meso-Aryl-Substituted Expanded Porphyrin

Synthesis and Biradicaloid Character of Doubly Linked Corrole Dimers

Directly linked corrole dimer 1, which has a planar cyclooctatetraene in its core, has been synthesized from 2-borylcorrole in excellent yield. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of 1 provides its oxidized form 4, which has two NH protons in each corrole core. Dicorrole 4 and its Zn(II) complex 6 exhibit broad electronic absorption spectra, and magnetic measurement has revealed their biradicaloid character

Synthesis and Biradicaloid Character of Doubly Linked Corrole Dimers

Directly linked corrole dimer 1, which has a planar cyclooctatetraene in its core, has been synthesized from 2-borylcorrole in excellent yield. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of 1 provides its oxidized form 4, which has two NH protons in each corrole core. Dicorrole 4 and its Zn(II) complex 6 exhibit broad electronic absorption spectra, and magnetic measurement has revealed their biradicaloid character

Synthesis and Biradicaloid Character of Doubly Linked Corrole Dimers

Directly linked corrole dimer 1, which has a planar cyclooctatetraene in its core, has been synthesized from 2-borylcorrole in excellent yield. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of 1 provides its oxidized form 4, which has two NH protons in each corrole core. Dicorrole 4 and its Zn(II) complex 6 exhibit broad electronic absorption spectra, and magnetic measurement has revealed their biradicaloid character

Homo- and Heterobismetal Complexes of 5-Hydroxy-10,15,25,30-tetrakis(pentafluorophenyl)-Substituted [26]Hexaphyrin(1.1.1.1.1.1)

Metalation of meso-free 5,10,20,25-tetrakis(pentafluorophenyl)-substituted [26]hexaphyrin(1.1.1.1.1.1) (4) with CuII and ZnII ions afforded homodinuclear complexes 6 and 7, respectively. A demetalation−remetalation protocol provided monozinc(II) complex 9 selectively, from which copper(II)−zinc(II) heterodinuclear complex 10 was prepared effectively

Homo- and Heterobismetal Complexes of 5-Hydroxy-10,15,25,30-tetrakis(pentafluorophenyl)-Substituted [26]Hexaphyrin(1.1.1.1.1.1)

Metalation of meso-free 5,10,20,25-tetrakis(pentafluorophenyl)-substituted [26]hexaphyrin(1.1.1.1.1.1) (4) with CuII and ZnII ions afforded homodinuclear complexes 6 and 7, respectively. A demetalation−remetalation protocol provided monozinc(II) complex 9 selectively, from which copper(II)−zinc(II) heterodinuclear complex 10 was prepared effectively

Synthesis, Electrochemical Behavior, and Catalytic Activity of Cobalt Complexes of 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids

A one-pot synthesis of cobalt­(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrins (CoTADAPs) from the corresponding 5-aryl-1-arylamino-9-chlorodipyrrins and cobalt­(II) acetate is reported. The CoTADAPs exhibited characteristic electrochemical behavior and catalyzed the intramolecular cyclization of N-benzyl-N-Boc-3-diazopropan-1-amines, probably via σ-CoIII–alkyl radical intermediates

<i>Meta</i>–<i>Para</i>-Linked Octaaza[1₈]cyclophanes and Their Polycationic States

Octaazacyclophanes, octaaza­[1₈]<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>-cyclophane (<b>2</b>) and octaaza­[1₈]<i>m</i>,<i>p</i>,<i>p</i>,<i>p</i>,<i>m</i>,<i>p</i>,<i>p</i>,<i>p</i>-cyclophane (<b>3</b>), as ring-size extended congeners of tetraaza­[1₄]<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>-cyclophane were synthesized, and the electronic states of their polycationic species were investigated by quantum chemical calculations, electrochemical measurements (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)), UV–vis–NIR spectroelectrochemical measurements, and pulsed electron spin resonance (ESR) spectroscopy. These octaazacyclophanes exhibited multiredox activities depending on different linkage patterns along the macrocyclic molecular skeletons, and both molecules were oxidizable up to their respective octacations. Spectroelectrochemical measurements demonstrated that <i>p</i>-phenylenediamine (PD) moieties in <b>2</b> could be converted from the semiquinoidal structure to the quinoidal sturcture with increasing oxidation number, whereas higher oxidation states of <b>3</b> did not show definite quinoidal deformation of PD moieties. A pulsed ESR spectrum gave evidence about formation of the almost pure spin-triplet state for <b>3</b>²⁺, whereas the high-spin states of <b>2</b>²⁺ and <b>2</b>⁴⁺ are virtually degenerate with the competing low-spin states even at low temperatures, probably due to the fragility of spin-coupling pathway caused by facile conformational changes