Chiroptical switching of molecular universal joint triggered by complexation/release of a cation: A stepwise synergistic complexation
Chiroptical switching of molecular universal joint triggered by complexation/release of a cation: A stepwise synergistic complexation
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DOI：
10.1016/j.cclet.2022.05.072
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发表时间：
2022-05
影响因子：
9.1
通讯作者：
Fanrui Gao;Xingke Yu;Ling Liu;Jinlei Chen;Yongjun Lv;Ting Zhao;Jie Ji;Jiabin Yao;Wanhua Wu;Cheng Yang
中科院分区：
文献类型：
--
作者：
Fanrui Gao;Xingke Yu;Ling Liu;Jinlei Chen;Yongjun Lv;Ting Zhao;Jie Ji;Jiabin Yao;Wanhua Wu;Cheng Yang
合成了含稠合冠醚子环（MUJ 1和MUJ 3）和不含醚氧原子环（MUJ 2）的柱[5]芳烃分子万向接头（MUJ），并对其进行了对映体区分.观察到冠醚fusedMUJsupon的等效阳离子Na+的添加显着的手性反转，显示各向异性（g）因子为0.014，而烷基子环fusedMUJ 2显示没有CD反转。首次证实了钠离子引发的子环向柱[5]芳烃空腔的滚入运动，阳离子-π相互作用和C单键H···π相互作用的协同非共价作用是稳定自包构象的原因.加入MeOH或竞争性主体15-冠-5醚后，MUJ 1与Na+的复合物被分解，随后子环被推出，这使得钠离子触发的手性光转换可逆。
Pillar[5]arene-based molecular universal joints (MUJs), bearing fused crown ether subring (MUJ1andMUJ3) or a ring without ether oxygen atom (MUJ2), were synthesized and enantio‑differentiated. Significant chiral inversion was observed for the crown ether-fusedMUJsupon the addition of equivalent cations Na+, showing an anisotropy (g) factor of 0.014, while alkyl subring-fusedMUJ2showed no CD inversions. Unprecedentedly, sodium ion triggered rolling-in motion of the subring to the pillar[5]arene cavity was verified, and the synergistic noncovalent interaction of cation-πinteractions and Csingle bondH···πinteractions were responsible for the stabilized self-included conformers. The addition of MeOH or competitive hosts 15-crown-5 ether disassembled the complex ofMUJ1and Na+followed by a rolling-out of the subring, which made the sodium-ion triggered chiroptical switching reversible.