Peripherally Hexasulfanylated Subporphyrins. Issue 7 (15th April 2015)

• Record Type: Journal Article
• Authors: Yoshida, Kota; Osuka, Atsuhiro
• Is Part Of: Chemistry, an Asian journal. Volume 10:Issue 7(2015:Jul.)
• Page Start: 1526
• Page End: 1534
• Publication Date: 2015-04-15
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201500225
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Peripherally hexachlorinated <italic>meso</italic>‐triphenyl subporphyrin <bold>4</bold> was prepared by chlorination of <italic>meso</italic>‐triphenyl subporphyrin <bold>1</bold> with <italic>N</italic>‐chlorosuccinimide and was effectively transformed to hexasulfanylated subporphyrins <bold>5</bold>–<bold>8</bold> via nucleophilic aromatic substitution (S_NAr) reactions with the corresponding thiols under basic conditions. The structures of <bold>5</bold>–<bold>8</bold> have been all well characterized by single‐crystal X‐ray analysis. ¹H NMR studies indicated that the <italic>meso</italic>‐phenyl substituents undergo restricted rotation for <bold>5</bold>–<bold>8</bold>, while the β‐sulfanyl substituents are conformationally flexible in <bold>5</bold>, <bold>6</bold>, and <bold>8</bold>, and are strictly regulated to an anti‐conformation in <bold>7</bold>. Judging from the absorption spectra, the oxidation and reduction potentials, and the DFT calculations, the substituent effects decrease in the order of <bold>5</bold>&gt;<bold>6</bold>&gt;<bold>7</bold>&gt;<bold>8</bold>. Subporphyrin <bold>8</bold> effectively captures C₆₀ in a 1:1 manner in [D₈]toluene solution.</p> </abstract>