Pnictogen bonding with alkoxide cages: which pnictogen is best?

Pnictogen bonding with alkoxide cages: which pnictogen is best?
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氮元素与醇盐笼键合:哪种氮元素最好?

DOI:
10.1039/c9nj03648b
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发表时间:
2019
影响因子:
3.3
通讯作者:
Cozzolino, Anthony F.
Cozzolino, Anthony F.
中科院分区:
化学3区
文献类型:
--
作者:
Trubenstein, Henry J.;Moaven, Shiva;Vega, Maythe;Unruh, Daniel K.;Cozzolino, Anthony F.

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氮族元素成键作为一种有用的超分子相互作用开始出现。这些系统的设计策略仍处于开发的早期阶段,人们的注意力主要集中在较轻的氮氧化物上。氮族元素键供体可以具有多达三个独立的结合位点,这可以导致三氮族元素键合。这已经在锑醇盐笼的自组装中观察到,但不是与较轻的同系物。这项工作报告了类似的砷醇盐笼,从事在一个单一的磷族元素键和铋同系物的合成探索的结构表征。DFT计算用于评估结构之间的差异。最终,氮族元素上的部分电荷和氮族元素孤对电子的能量决定了这些笼形成的氮族元素键的强度、方向和数量。锑笼在强度和方向性之间取得了最佳平衡,使它们能够实现其他同系物无法实现的三重氮族元素键合。
Pnictogen bonding is beginning to emerge as a useful supramolecular interaction. The design strategies for these systems are still in the early stages of development and much attention has been focused on the lighter pnictogens. Pnictogen bond donors can have up to three independent sites for binding which can result in triple pnictogen bonding. This has been observed in the self-assembly of antimony alkoxide cages, but not with the lighter congeners. This work reports structural characterization of an analogous arsenic alkoxide cage that engages in a single pnictogen bond and synthetic explorations of the bismuth congener. DFT calculations are used to evaluate the differences between the structures. Ultimately the partial charge on the pnictogen and the energy of the pnictogen lone pair dictate the strength, orientation and number of pnictogen bonds that these cages form. Antimony cages strike the best balance between strength and directionality, allowing them to achieve triple pnictogen bonding where the other congeners do not.
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