meso-Aryl substituted stable unorthodox 5,10-porphodimethenes with α,β and β,β-N-methyl pyrrole connectivities: synthesis and spectroscopic, solid state and theoretical characterization

Abstract

meso-Aryl substituted highly stable single conformers of doubly mutant porphodimethenes.

Chemical transformation of doubly N-confused porphodimethenes to variants of (anti)aromatic doubly N-confused porphyrinoids and σ-aromatic doubly N-confused isophlorinoids

“…In line with the expected electronic absorption spectrum of porphodimethene, 17 6 comprises two absorption bands, one at 316 nm and the other at 493 nm (Fig. 1A), while for 7 (Fig.…”

“…Given the focus of our present study, we adopted [3 + 1] acid catalysed conventional oxidative condensation of N-confused N-methyl tripyrrane 5 and N-confused N-methyl dicarbinol 4 using p-toluene sulfonic acid ( p-TSA) followed by subsequent oxidation using 1.5 equivalent chloranil as shown in Scheme 1. 17 Under this reaction strategy, we anticipated the isolation of non-aromatic doubly N-confused oxocalix [4]phyrin 6 as the major product and doubly N-confused calix[5]phyrin 7 as the minor product. Column chromatographic separation over basic alumina followed by repeated silica gel (200-400 mesh) chromatographic separation and preparative thin layer chromatography (PTLC) techniques led to the isolation of air stable 6 in 40% yield as a green solid and 7 in 4% yield as a brown solid.…”

Comparative in vitro Studies of the Topoisomerase I Inhibition and Anticancer Activities of Metallated N‐Confused Porphyrins and Metallated Porphyrins

“…In the next step, all three macrocycles were metallated with copper and zinc salts for the formation of metallated complexes 2, 3, 5, 6, 8, 9 following literature method. [47][48][49][50][51][52] Macrocycle 13 was synthesized following literature known method [53] and the respective copper and zinc complexes 14 and 15 were synthesized following literature known methods. [36,54] The UV-vis absorption spectra, NMR spectra and chemical analysis of all the macrocycles (both in free base forms and zinc-complexes) are well consistent with the proposed structures.…”

Tailor-made aromatic porphyrinoids with NIR absorption

“…34) via p -toluenesulfonic acid ( p -TSA) catalysed acidolysis of N-confused N-methyl tripyrrane P166 and subsequent chloranil oxidation. 79 Rath et al further unravelled the viability of metallated (Zn and Cu) N-confused porphyrins 168 / 169 (Fig. 34) to stabilize the topoisomerase–DNA covalent complex due to minor groove binding.…”