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Persulfurated Benzene‐Cored Asterisks with π‐Extended ThioNaphthyl Arms: Synthesis, Structural, Photophysical and Covalent Dynamic Properties
Author(s) -
Gahlot Sapna,
Gradone Alessandro,
Roy Myriam,
Giorgi Michel,
Conti Simone,
Ceroni Paola,
Villa Marco,
Gingras Marc
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200797
Subject(s) - phosphorescence , benzene , photochemistry , chemistry , naphthalene , phosphor , sulfur , materials science , organic chemistry , fluorescence , physics , optoelectronics , quantum mechanics
Abstract The synthesis of regioisomeric asterisks ( 5 ) and ( 6 ) incorporating a benzene core with six 1‐naphthylthio or six 2‐naphthylthio arms are reported in search for new materials with optoelectronic properties. The consequences on the extension of a π system surrounding a persulfurated benzene core provide a new avenue to study the structural, photophysical, and chemical properties of such family of all‐organic phosphors. It also diverts the persulfuration mechanism after two radical cyclizations for making a [5]dithiohelicene by‐product ( 7 ) and favors dynamic sulfur component exchange reactions surrounding the core. These exchanges convert asterisks ( 5 ) and ( 6 ), non‐phosphorescent at 20 °C to the highly phosphorescent ( 4 ) ( ϕ ∼100 %, solid state at 20 °C). For asterisks ( 5 ) and ( 6 ), the absence of the typical phosphorescence of the per(phenylthio)benzene core in the solid state at 20 °C and the presence of a weak naphthalene‐based phosphorescence at 77 K is attributed to an energy transfer from the triplet state of the persulfurated benzene core to the outer naphthalene moieties, resulting in an antenna system.