Anisotropic Crystals Based on Main-group Coordination Polymer with Alignment of Rigid π-Skeletons
Anisotropic Crystals Based on Main-group Coordination Polymer with Alignment of Rigid π-Skeletons
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基于刚性π骨架配向主族配位聚合物的各向异性晶体
DOI：
10.1021/acs.organomet.7b00217
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发表时间：
2017
期刊：
影响因子：
2.8
通讯作者：
M. Hada and H. Y. Yoshikawa
中科院分区：
文献类型：
--
作者：
M. Saito;T. Akiba;S. Furukawa;M. Minoura;M. Hada and H. Y. Yoshikawa
我们成功地排列了π骨架，从而形成了各向异性晶体。将二价铅原子引入π骨架中的铅环戊二烯亚基与1，4-二氧六环结合得到π骨架完全沿同一方向排列的配位聚合物。所得到的亚铅链在固态下也沿相同方向排列，因此晶体是非中心对称的，显示出二次谐波产生（SHG）特性。用吡嗪代替1，4-二氧六环得到了由三个铅原子和两个吡嗪分子组成的加合物，晶体对称，无倍频现象。固态结构和光学性质高度依赖于所用的刘易斯碱。本发明的发现突出了将第14族二价物质并入π骨架中作为用于产生具有NLO性质的π-对准配位聚合物的新颖有用的方法的用途。
We succeeded in the alignment of π skeletons, resulting in the formation of anisotropic crystals. The combination of plumbacyclopentadienylidene, which has a divalent lead atom incorporated into the π skeleton, and 1,4-dioxane afforded a coordination polymer, where the π 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 π skeleton as a novel, useful method for the creation of a π-aligned coordination polymer with NLO properties.