Application of Long-Range Synthon Aufbau Modules Based on Trihalophenols To Direct Reactivity in Binary Cocrystals: Orthogonal Hydrogen Bonding and π-π Contact Driven Self-Assembly with Single-Crystal Reactivity
Application of Long-Range Synthon Aufbau Modules Based on Trihalophenols To Direct Reactivity in Binary Cocrystals: Orthogonal Hydrogen Bonding and π-π Contact Driven Self-Assembly with Single-Crystal Reactivity
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DOI：
10.1021/acs.cgd.9b00035
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发表时间：
2019-05-01
影响因子：
3.8
通讯作者：
MacGillivray, Leonard R.
中科院分区：
文献类型：
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作者：
Campillo-Alvarado, Gonzalo;Li, Changan;MacGillivray, Leonard R.
报道了2,4,6-三卤酚（3X-phOH）（其中X = F， Cl或Br）在固态下通过共结晶使1,2-二（4-吡啶基）乙烯（bpe）具有反应活性的能力。三卤酚显示出由无限面对面pi定义的结构行为。作为纯固体的PI接触和氢键可以转移到二元共晶中组织bpe进行固态光二聚化。基于Cl-和br -卤代酚的共晶通过单晶到单晶的光反应得到立体选择性的四烷基（4-吡啶基）环丁烷（tpcb），产量接近定量。在远程合成Aufbau模块的背景下，讨论了使用3X-phOH在固态中实现反应性。
The ability of 2,4,6-trihalophenols (3X-phOH) (where X = F, Cl, or Br) to enable reactivity of 1,2-bis(4-pyridyl)ethylene (bpe) in the solid state via cocrystallization is reported. The trihalophenols display structure behavior defined by infinite face-to-face pi...pi contacts and hydrogen bonds as pure solids that we show can be transferred to binary cocrystals to organize bpe to undergo a solid-state photodimerization. Cocrystals based on Cl- and Br-halophenols undergo single-crystal-to single-crystal photoreactions to afford rctt-tetrakis(4-pyridyl)cyclobutane (tpcb) stereoselectively and in near quantitative yield. The use of 3X-phOH to enable reactivity in the solid state is discussed in the context of long-range synthon Aufbau modules.