A Parallel-Displaced Directly Linked 21-Carba-23-Thiaporphyrin Dimer Incorporating a Dihydrofulvalene Motif

Anna Berlicka; Michał J Białek; Lechosław Latos-Grażyński

doi:10.1002/anie.201606298

A Parallel-Displaced Directly Linked 21-Carba-23-Thiaporphyrin Dimer Incorporating a Dihydrofulvalene Motif

Angew Chem Int Ed Engl. 2016 Sep 5;55(37):11231-6. doi: 10.1002/anie.201606298. Epub 2016 Aug 17.

Authors

Anna Berlicka¹, Michał J Białek¹, Lechosław Latos-Grażyński²

Affiliations

¹ Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., 50-383, Wrocław, Poland.
² Department of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., 50-383, Wrocław, Poland. lechoslaw.latos-grazynski@chem.uni.wroc.pl.

PMID: 27530897
DOI: 10.1002/anie.201606298

Abstract

In the search of porphyrin arrays with a unique geometry, the efficient synthesis of a directly linked 21-carba-23-thiaporphyrin dimer with the distinctive dihydrofulvalene bridging motif has been developed. This compound acquires an uncommon parallel-displaced arrangement of two carbaporphyrin planes. The dimer undergoes an acid-triggered cleavage to create of the asymmetric carbathiaporphyrin-carbathiachlorin dyad or 2,3-dihalo-21-carba-23-thiachlorin depending on choice of acid. A formation of a reactive carbocation intermediate is postulated to account for mechanism of cleavage.

Keywords: NMR spectroscopy; carbaporphyrinoids; cleavage reactions; dimerization; dimers.

Publication types

Research Support, Non-U.S. Gov't