Triple-Pnictogen Bonding as a Tool for Supramolecular Assembly
Triple-Pnictogen Bonding as a Tool for Supramolecular Assembly
复制标题
三磷键合作为超分子组装的工具
DOI：
10.1021/acs.inorgchem.9b02761
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发表时间：
2019
影响因子：
4.6
通讯作者：
Cozzolino, Anthony F.
中科院分区：
文献类型：
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作者：
Moaven, Shiva;Andrews, Miranda C.;Polaske, Thomas J.;Karl, Brian M.;Unruh, Daniel K.;Bosch, Eric;Bowling, Nathan P.;Cozzolino, Anthony F.
通过 X 射线晶体学、溶液核磁共振和计算化学，探索了利用在单个锑顶点周围同时形成三个磷元素键的超分子组装。芳基乙炔基 (AE) 配体旨在补充 Sb 化合物周围的三个亲电子区域。尽管溶液研究揭示了单个吡啶基单元与 Sb 供体的较大结合常数，但 AE 受体的刚性和预排列被证明是实现三个受体与以 Sb 为中心的磷元素键供体同时结合所必需的。计算和 X 射线结构表明，三个受体顺序结合到 Sb 中心时的负协同性限制了三磷元素键合吡啶基受体的实用性。然而，当将正协同性设计到互补受体配体中时，这些限制就可以被消除。
Supramolecular assembly utilizing simultaneous formation of three pnictogen bonds around a single antimony vertex was explored via X-ray crystallography, solution NMR, and computational chemistry. An arylethynyl (AE) ligand was designed to complement the three electrophilic regions around the Sb compound. Though solution studies reveal large binding constants for individual pyridyl units with the Sb donor, the rigidity and prearrangement of the AE acceptor proved necessary to achieve simultaneous binding of three acceptors to the Sb-centered pnictogen-bond donor. Calculations and X-ray structures suggest that negative cooperativity upon sequential binding of three acceptors to a Sb center limits the utility of triple-pnictogen bonding pyridyl acceptors. These limitations can be negated, however, when positive cooperativity is designed into a complementary acceptor ligand.