Anisotropic Crystals Based on a Main-Group Coordination Polymer with Alignment of Rigid pi Skeletons

作者：Saito Masaichi^*; Akiba Tomoki; Furukawa Shunsuke; Minoura Mao; Hada Masahiko; Yoshikawa Hiroshi Y

来源：Organometallics, 2017, 36(14): 2487-2490.

DOI：10.1021/acs.organomet.7b00217

We succeeded in the alignment of pi skeletons, resulting in the formation of anisotropic crystals. The combination of plumbacyclopentadienylidene, which has a divalent lead atom incorporated into the pi skeleton, and 1,4dioxane afforded a coordination polymer, where the Jr skeletons are completely aligned in the same direction. The resulting plumbylene chains are also aligned in the same direction in the solid state, and therefore the crystals are noncentrosymmetric, showing second-harmonic generation (SHG) properties. Using pyrazine instead of 1,4-dioxane afforded an adduct composed of three plumbole units and two pyrazine molecules, and the crystals are symmetric and exhibit no SHG properties. The solid-state structures and optical properties are highly dependent on the Lewis base utilized. The present findings spotlight the use of group 14 divalent species incorporated into a pi skeleton as a novel, useful method for the creation of a pi-aligned coordination polymer with NLO properties.

• 出版日期2017-7-24