Departamento de Química Física, Facultad de Ciencias Ambientales y Bioquímica, and INAMOL, Universidad de Castilla-La Mancha, Avenida Carlos III, S/N, 45071 Toledo, Spain.
Division of Chemistry, Graduate School of Engineering Science, Osaka University, Osaka 565-0871, Japan.
Int J Mol Sci. 2022 Feb 9;23(4):1929. doi: 10.3390/ijms23041929.
Hydrogen-bonded organic frameworks (HOFs) have attracted renewed attention as another type of promising candidates for functional porous materials. In most cases of HOF preparation, the applied molecular design principle is based on molecules with rigid π-conjugated skeleton together with more than three H-bonding groups to achieve 2D- or 3D-networked structures. However, the design principle does not always work, but results in formation of unexpected structures, where subtle structural factors of which we are not aware dictate the entire structure of HOFs. In this contribution, we assess recent advances in HOFs, focusing on those composed of hexatopic building block molecules, which can provide robust frameworks with a wide range of topologies and properties. The HOFs described in this work are classified into three types, depending on their H-bonded structural motifs. Here in, we focus on: (1) the chemical aspects that govern their unique fundamental chemistry and structures; and (2) their photophysics at the ensemble and single-crystal levels. The work addresses and discusses how these aspects affect and orient their photonic applicability. We trust that this contribution will provide a deep awareness and will help scientists to build up a systematic series of porous materials with the aim to control both their structural and photodynamical assets.
氢键有机框架（HOFs）作为另一种有前途的功能多孔材料候选者，重新引起了人们的关注。在大多数 HOF 制备的情况下，应用的分子设计原理基于具有刚性π共轭骨架和超过三个氢键基团的分子，以实现 2D 或 3D 网络结构。然而，设计原理并不总是有效，反而会导致形成意想不到的结构，我们不知道的细微结构因素决定了 HOF 的整个结构。在本贡献中，我们评估了 HOF 的最新进展，重点关注由六配位构筑块分子组成的 HOF，它们可以提供具有广泛拓扑和性质的坚固框架。本文所述的 HOF 分为三种类型，取决于它们的氢键结构基序。在这里，我们重点关注：（1）控制其独特基础化学和结构的化学方面；以及（2）它们在整体和单晶水平上的光物理性质。这项工作解决并讨论了这些方面如何影响和确定它们的光子适用性。我们相信，这一贡献将提供深刻的认识，并帮助科学家构建一系列系统的多孔材料，以控制其结构和光动力学资产。
