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An Iodine‐Vapor‐Induced Cyclization in a Crystalline Molecular Flask
Author(s) -
Knichal Jane V.,
Shepherd Helena J.,
Wilson Chick C.,
Raithby Paul R.,
Gee William J.,
Burrows Andrew D.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201601525
Subject(s) - iodine , chemistry , solvent , yield (engineering) , naphthalene , photochemistry , medicinal chemistry , organic chemistry , materials science , metallurgy
A vapor‐induced cyclization has been observed in the host environment of a crystalline molecular flask (CMF), within which 1,8‐bis(2‐phenylethynyl)naphthalene (bpen), a diarenynyl system primed for cyclization, was exposed to iodine vapor to yield the corresponding indeno[2,1‐α]phenalene species. The cyclization process, unique in its vapor‐induced, solvent‐free nature, was followed spectroscopically, and found to occur concurrently with the displacement of lattice solvent for molecular iodine in CMF⋅0.75 bpen⋅2.25 CHCl 3 ⋅H 2 O. The cyclization occurred under mild conditions and without the need to suspend the crystals in solvent. The ability of CMFs to host purely gas‐induced reactions is further highlighted by the subsequent sequential oxidation reaction of cyclized 7‐iodo‐12‐phenylindeno[2,1‐α]phenalene (ipp) with molecular oxygen derived from air, yielding 12‐hydroxy‐7‐iodo‐2‐phenylindeno[2,1‐α]phenalen‐1(12 H )‐one (hipp).