Photochromic Hybrid Containing <i>In Situ</i>-Generated Benzyl Viologen and Novel Trinuclear [Bi<sub>3</sub>Cl<sub>14</sub>]<sup>5–</sup>: Improved Photoresponsive Behavior
by the π···π Interactions and Size Effect
of Inorganic Oligomer
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Abstract
Two new member of (V)<sub>(2<i>n</i>+2)/2</sub>[Bi<sub>2<i>n</i></sub>Cl<sub>8<i>n</i>+2</sub>] series hybrids, (BzV)<sub>2</sub>[Bi<sub>2</sub>Cl<sub>10</sub>] (<b>1</b>) and (BzV)<sub>5</sub>[Bi<sub>3</sub>Cl<sub>14</sub>]<sub>2</sub>·(C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>)<sub>2</sub>O (<b>2</b>) (where BzV<sup>2+</sup> = <i>N</i>,<i>N</i>′-dibenzyl-4,4′-bipyridinium
and (C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>)<sub>2</sub>O = dibenzyl
ether) have been obtained, and compound <b>2</b> contains an
unprecedented discrete trimer [Bi<sub>3</sub>Cl<sub>14</sub>]<sup>5–</sup> counterion. The novel <i>in situ</i>-synthesized
symmetric viologen cation with aromatic groups on both sides of 4,4′-bipy
would provide more opportunities to create π···π
interactions to optimize the photochromic property of the hybrid,
and different bismuthated-halide oligomers enable us to discuss the
size effect in this series of compounds. Both <b>1</b> and <b>2</b> are photochromic, and their photoresponsive rate is faster
than that of reported viologen–metal halide hybrids. Experimental
and theoretical data illustrated that the size of the inorganic oligomer
can significantly influence the photoresponsive rate of the viologen
dication, and the π···π interaction behaves
as not only a powerful factor to stabilize the viologen monocation
radical but also the second electron-transfer pathway, from a π-conjugated
substituent to a viologen cation, for the photochromic process