Unusual Twisting and Bending of Phenyltriene with Methylthiolated Biphenyl Sulfane Group in the Crystalline State

We report a series of π-conjugated phenyltriene
analogous
molecules and crystals having different thiolated building blocks,
which significantly influence the molecular ordering in the crystalline
state. Whereas a polyene crystal having the methylthiolated phenyl
(SM) building block exhibits a zigzag molecular ordering based on
head-to-tail hydrogen bonds, the crystals of other analogues having
the biphenyl sulfane (SB) block exhibit isomorphic crystal structures
with herringbone packing. In one of these isomorphic crystals having
both SM and SB building blocks, the herringbone packing is accompanied
with head-to-tail hydrogen bonds. As a result of such packing promoted
by SM and SB building blocks, the rigid phenyltriene bridge shows
an unusual twisting and bending conformation, which is accompanied
with a significant change of physical properties, such as fluorescent,
linear, and nonlinear optical properties in the solid state.