Department of Chemistry, Colorado School of Mines, Golden, Colorado 80401, United States.
Department of Chemistry and Chemistry Research Center, Laboratories for Advanced Materials, United States Air Force Academy, Colorado Springs, Colorado 80840, United States.
J Am Chem Soc. 2021 Dec 8;143(48):20207-20215. doi: 10.1021/jacs.1c08642. Epub 2021 Nov 24.
The manner of bonding between constituent atoms or molecules invariably influences the properties of materials. Perhaps no material family is more emblematic of this than porous frameworks, wherein the namesake modes of connectivity give rise to discrete subclasses with unique collections of properties. However, established framework classes often display offsetting advantages and disadvantages for a given application. Thus, there exists no universally applicable material, and the discovery of alternative modes of framework connectivity is highly desirable. Here we show that chalcogen bonding, a subclass of σ-hole bonding, is a viable mode of connectivity in low-density porous frameworks. Crystallization studies with the triptycene tris(1,2,5-selenadiazole) molecular tecton reveal how chalcogen bonding can template high-energy lattice structures and how solvent conditions can be rationalized to obtain molecularly programmed porous chalcogen-bonded organic frameworks (ChOFs). These results provide the first evidence that σ-hole bonding can be used to advance the diversity of porous framework materials.
构成原子或分子之间的键合方式总是会影响材料的性质。也许没有哪种材料家族比多孔骨架更能体现这一点，因为其命名的连接模式产生了具有独特属性组合的离散子类。然而，对于给定的应用，已建立的骨架类通常具有相互抵消的优缺点。因此，不存在普遍适用的材料，而发现替代的骨架连接模式是非常需要的。在这里，我们表明，硫属键合（σ-hole bonding 的一个子类）是低密度多孔骨架中可行的连接模式。使用三并苯三（1,2,5-硒二唑）分子构筑块进行的结晶研究揭示了硫属键合如何可以模板高能晶格结构，以及如何合理控制溶剂条件以获得分子编程的多孔硫属键合有机骨架（ChOFs）。这些结果提供了第一个证据，证明σ-hole bonding 可用于推动多孔骨架材料的多样性。
