Synthesis of amphiphilic chiral salen complexes and their conformational manipulation at the air-water interface
Synthesis of amphiphilic chiral salen complexes and their conformational manipulation at the air-water interface
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两亲手性萨伦配合物的合成及其在空气-水界面的构象操纵
DOI：
10.1039/d2dt03201e
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发表时间：
2023
影响因子：
4
通讯作者：
Katsuhiko Ariga
中科院分区：
文献类型：
--
作者：
Shigehisa Akine;Keisuke Nomura;Mizuho Takahashi;Yoko Sakata;Taizo Mori;Waka Nakanishi;Katsuhiko Ariga
设计并合成了一系列两亲性salen配合物[L1 a，bM]和[L2 a，bM]。这些配合物由两个或四个亲水性三甘醇（TEG）链和基于萘或菲的疏水性π-延伸的金属salen核组成。所得的两亲性配合物[L1 bM]（M = Ni，Cu，Zn）在空气-水界面上形成单分子膜，而单阳离子[L1 bCo（MeNH 2）2]（OTf）在空气-水界面上没有形成明确的单分子膜.亲水性TEG链的数量也对单层形成行为有影响;四-TEG衍生物[L1 bNi]和[L2 bNi]在比双-TEG衍生物[L1 aNi]和[L2 aNi]压缩更小的区域显示出压力升高。此外，它们的压缩性和压缩模量的研究表明，四-TEG衍生物，[L1 bNi]和[L2 bNi]，是更灵活的比相应的bis-TEG类似物，[L1 aNi]和[L2 aNi]，和菲衍生物[L1 a，bNi]是更刚性比相应的萘类似物，[L2 a，bNi]。其中一种配合物[L1 bNi]的LB膜的CD谱与溶液中的略有不同，这可能是由于空气-水界面独特的各向异性环境造成的。因此，我们证明了通过机械压缩来控制金属配合物的手性光学性质的可能性。
A series of amphiphilic salen complexes, [L1a,bM] and [L2a,bM], were designed and synthesized. These complexes consist of two or four hydrophilic triethylene glycol (TEG) chains and a hydrophobic π-extended metallosalen core based on naphthalene or phenanthrene. The obtained amphiphilic complexes, [L1bM] (M = Ni, Cu, Zn), formed a monolayer at the air–water interface, while the monocationic [L1bCo(MeNH2)2](OTf) did not form a well-defined monolayer. The number of hydrophilic TEG chains also had an influence on the monolayerformation behavior; the tetra-TEG derivatives, [L1bNi] and [L2bNi], showed a pressure rise at a less compressed region than the bis-TEG derivatives, [L1aNi] and [L2aNi]. In addition, the investigation of their compressibility and compression modulus suggested that the tetra-TEG derivatives, [L1bNi] and [L2bNi], are more flexible than the corresponding bis-TEG analogues, [L1aNi] and [L2aNi], and that the phenanthrene derivatives [L1a,bNi] were more rigid than the corresponding naphthalene analogues, [L2a,bNi]. The Langmuir–Blodgett (LB) films of one of the complexes, [L1bNi], showed CD spectra slightly different from that in solution, which may originate from the unique anisotropic environment of the air–water interface. Thus, we demonstrated the possibility of controlling the chiroptical properties of metal complexes by mechanical compression.