Ohtani Ryo, Yamamoto Riho, Ohtsu Hiroyoshi, Kawano Masaki, Pirillo Jenny, Hijikata Yuh, Sadakiyo Masaaki, Lindoy Leonard F, Hayami Shinya
Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.
Dalton Trans. 2019 May 28;48(21):7198-7202. doi: 10.1039/c8dt04624g.
The 2D coordination polymers, [Mn(salen)]2[PtII(CN)4]1-x[PtIV(CN)4(I2)]x (salen = N,N'-ethylenebis(salicylideneaminato), x = 0.18 (1), 0.45 (2), 0.85 (3)), have been synthesized via consecutive oxidative additions of iodine to the 2D undulating layers in [Mn(salen)]2[PtII(CN)4]. The presence of I-Pt-I chains perpendicular to the layers and the inhomogeneity of individual I-Pt-I sites were demonstrated. The I-Pt-I chains in 3 give rise to an absorption band involving the excitation that arises from an antibonding nature orbital to the corresponding bonding nature orbital between iodides in the I-Pt-I bridging units. Moreover, variable-temperature X-ray powder diffraction patterns and Raman spectra for 1 and 2 indicate that some I-Pt-I sites display different vibrational energies that are associated with the contraction of the zigzag 2D layers.
二维配位聚合物[Mn(salen)]2[PtII(CN)4]1-x[PtIV(CN)4(I2)]x（salen = N,N'-亚乙基双（水杨醛氨基），x = 0.18 (1)、0.45 (2)、0.85 (3)）是通过碘连续氧化加成到[Mn(salen)]2[PtII(CN)4]中的二维起伏层而合成的。证明了存在垂直于层的I-Pt-I链以及各个I-Pt-I位点的不均匀性。化合物3中的I-Pt-I链产生一个吸收带，该吸收带涉及从I-Pt-I桥连单元中碘化物之间的反键性质轨道到相应成键性质轨道的激发。此外，化合物1和2的变温X射线粉末衍射图谱和拉曼光谱表明，一些I-Pt-I位点显示出与锯齿形二维层收缩相关的不同振动能量。
