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.