Coordination Amphiphile: Design of Planar-Coordinated Platinum Complexes for Monolayer Formation at an Air-Water Interface Based on Ligand Characteristics and Molecular Topology
Coordination Amphiphile: Design of Planar-Coordinated Platinum Complexes for Monolayer Formation at an Air-Water Interface Based on Ligand Characteristics and Molecular Topology
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DOI：
10.1246/bcsj.20220086
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发表时间：
2022-06-01
影响因子：
4
通讯作者：
Mori, Taizo
中科院分区：
文献类型：
--
作者：
Adachi, Junya;Naito, Masaya;Mori, Taizo
我们的目标是在基于配体特征和分子拓扑的配位两亲性概念下，确定分子设计对于在空气-水界面形成单分子层的重要性。为此，合成了5种含配位平面的铂配合物，包括水杨醛(SA)和β-(亚氨甲基)氮杂环(IA)配合物，其中配体的性质是可控的。然后考察了聚亚甲基拱顶和非拱顶的络合物，以评估分子拓扑对界面活性的影响。SA络合物倾向于在空气-水界面进行随机聚集，而SA的弱亲水性有助于形成稳定的单分子膜，如果在结构中引入疏水和亲水链。相反，IA络合物表现出拓扑特异性；咪唑和吡唑络合物仅对非拱形和拱形络合物形成单分子膜。分子模拟和缔合常数表明，配位平面的亲水性和涉及氢键的分子间相互作用是形成单分子膜的重要因素。
We aim to establish the importance of molecular design for the formation of monolayers at an air-water interface within the concept "coordination amphiphile", which is based on ligand characteristics and molecular topology. For this purpose, five types of platinum complexes containing a coordination plane, including salicylaldiminato (SA) and beta-(iminomethyl)azolato (IA) complexes, were prepared where the ligand characteristics were controlled. Polymethylene-vaulted and non-vaulted complexes were then examined to assess the effects of molecular topology on interfacial activity. SA complexes tend to undergo random aggregation at an air-water interface, while the weak hydrophilicity of SA can assist in the formation of a stable monolayer if hydrophobic and hydrophilic chains are introduced to the structure. In contrast, IA complexes exhibit topological specificity; imidazolato and pyrazolato complexes form monolayers only for non-vaulted and vaulted complex, respectively. Molecular modelling and association constants of the compounds suggest that an appropriate hydrophilicity of the coordination plane and intermolecular interactions involving hydrogen bonding are important factors for monolayer formation.