Entropy Versus Enthalpy Controlled Temperature/Redox Dual-Triggered Cages for Selective Anion Encapsulation and Release
Entropy Versus Enthalpy Controlled Temperature/Redox Dual-Triggered Cages for Selective Anion Encapsulation and Release
复制标题
用于选择性阴离子封装和释放的熵与焓控制温度/氧化还原双触发笼
DOI：
10.1002/ange.202113914
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Kyosuke Hamashima and Junpei Yuasa
中科院分区：
文献类型：
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作者：
Yoshihiro Owatari;Shuta Iseki;Daiji Ogata and Junpei Yuasa;Kyosuke Hamashima and Junpei Yuasa
新的C3对称咪唑配体被设计为具有膦和氧化膦连接体（分别为LPandLPO）以展示双触发的动态闭合配位笼。LPO和LPO都形成了独立的Zn 4L 4-封闭笼（分别为1 Pand 1 PO），对BPh 4 −有很好的选择性，其中1 Pand 1 PO既不包封稍大尺寸的阴离子[B（C6 H4 CH 3）4−]，也不包封较小尺寸的阴离子（BF 4 −、PF 6 −、SbF 6 −和OSO 2CF 3 −）。1 PO在阴离子包封时表现出更多的负焓和熵变，因此在高温（343 K）下几乎释放了所有包封的阴离子（触发1：BPh 4 − → 1 PO 1 PO + BPh 4 −）。 相比之下，1 P具有较小的负焓变和熵变，从而在很宽的温度范围内（298 K至343 K）保留捕获的阴离子。 1 Pcage可以被温和的氧化剂（Ox. H2 O2），因此捕获的阴离子可以通过氧化还原触发事件（触发2：BPh 4 − → 1 P +Ox.→ 1 PO + BPh 4 −）释放。
New C3‐symmetric imidazole ligands were designed with phosphine and phosphine oxide linkers (LPandLPO, respectively) to demonstrate a dual‐triggered dynamic closed coordination cage. BothLPandLPOform discrete Zn4L4‐closed cages (1Pand1PO, respectively) with excellent selectively for BPh4−, whereas1Pand1POencapsulate neither a slightly larger size anion [B(C6H4CH3)4−] nor smaller size anions (BF4−, PF6−, SbF6−, and OSO2CF3−).1POexhibits more negative enthalpy and entropy changes upon anion encapsulation, thus releasing almost all of the encapsulated anions at high temperature (343 K) (trigger 1: BPh4−⊂1PO1PO+BPh4−). In contrast1Phas less negative enthalpy and entropy changes, thus preserving the captured anion over a wide range of temperatures (298 K to 343 K). The1Pcage can be quantitatively oxidized to the1POcage by a mild oxidant (Ox.=H2O2), and therefore the captured anion can be released by a redox triggering event (trigger 2: BPh4−⊂1P+Ox.→1PO+BPh4−).