Synthesis of Platinum-Containing Conjugated Polymers Bearing Chiral Phosphine Ligands. Study of Geometries and Intermolecular Interactions Leading to Aggregation
Synthesis of Platinum-Containing Conjugated Polymers Bearing Chiral Phosphine Ligands. Study of Geometries and Intermolecular Interactions Leading to Aggregation
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DOI：
10.1021/acs.organomet.2c00173
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发表时间：
2022-06-22
期刊：
影响因子：
2.8
通讯作者：
Sanda, Fumio
中科院分区：
文献类型：
--
作者：
Makino, Soya;Horiuchi, Takashi;Sanda, Fumio
通过顺式和反式二氯双（N-（对二苯基膦基）苯甲酰基）-1-缬氨酸甲酯）合铂（II）{cis-PtL 2Cl 2和trans-PtL 2Cl 2，L = P（Ph）（2）-p-C6 H4 CONHCH [CH（CH 3）（2）] CO2 CH 3}与1，4-二乙炔基苯的脱氯化氢偶联聚合，合成了含铂共轭聚合物，目的是获得在铂中心具有可控几何构型的聚合物。在顺式PtL_2Cl_2的聚合反应中，Pt中心的几何构型由聚合反应中使用的胺和反应温度控制。在CH_2Cl_2/MeOH混合溶剂中，所形成的具有反式Pt中心的聚合物在主链发色团区域呈现圆二色性信号。基于模型化合物的晶体堆积状态和非共价相互作用分析，手光学活性归因于分子间pi-pi、CH-pi和膦配体之间的氢键相互作用稳定的聚集。
Platinum (Pt)-containing conjugated polymers were synthesized by the dehydrochlorination coupling polymerization of cis- and trans-dichlorobis(N-(p-(diphenylphosphino)benzoyl)-l-valine methyl ester)platinum(II) {cis-PtL2Cl2 and trans-PtL2Cl2, L = P(Ph)(2)-p-C6H4CONHCH[CH(CH3)(2)]CO2CH3} with 1,4-diethynylbenzene, aiming at obtaining polymers with controlled geometry at the Pt centers. In the polymerization of cis-PtL2Cl2, the geometry at the Pt centers was controlled by the amine used in the polymerization and the reaction temperature. The formed polymer with trans-Pt centers exhibited a circular dichroism signal at the main chain chromophore region in CH2Cl2/MeOH mixed solvent. Based on the crystal packing state and non-covalent interaction analysis of a model compound, the chiroptical activity is attributed to aggregation stabilized by intermolecular pi-pi, CH-pi, and hydrogen-bonding interactions between the phosphine ligands.