Overflowing metal–organic frameworks (MOFs) have been synthesized from a wide range of metal and organic components for specific purposes and intellectual curiosity. Each MOF has unique chemical and structural characteristics directed by the incorporated components, metal ions (or clusters), organic linkers, and their intrinsic coordination interactions. These incorporated components and structural characteristics are two pivotal factors influencing MOFs’ fundamental properties and subsequent applications. Therefore, selecting the appropriate metal and organic components, considering their innate chemical and structural properties, is crucial to endow the final MOFs with the desired properties. Ultimately, producing MOFs with a desired structure using ideal components is the best approach to achieving the best MOFs tailored for specific purposes with desired properties. However, achieving MOFs with the intended structure from chosen components remains underdeveloped. In many cases, the resulting MOF structure is governed by the thermodynamically and/or kinetically preferred configuration (refers to a naturally preferred structure) of the chosen components and given reaction conditions. Additionally, producing hybrid MOFs with complex components, structures, and morphologies presents a great opportunity to obtain special MOFs with advanced properties and functions. In this Account, we outline our group’s efforts over the past few years to develop naturally nonpreferred MOFs through the induced MOF-on-MOF growth process and atypical hybrid MOFs via nonstandard MOF-on-MOF growth. First, we highlight the prime strategy for producing naturally nonpreferred MOFs based on template-induced MOF-on-MOF growth. In this section, we discuss the two basic growth behaviors, isotropic and anisotropic growth of naturally nonpreferred MOFs, determined by the degree of matching between the cell lattices of the two MOFs. Second, we introduce the MOF farming concept for the productive cultivation and effective harvesting of naturally nonpreferred MOFs made by MOF-on-MOF growth. Here we discuss the importance of selecting the ideal MOF template for productive growth and developing an efficient method for harvesting cultivated MOFs. Next, we describe atypical anisotropic MOF-on-MOF growths between two MOFs with mismatched cell lattices. In this section, we introduce tip-to-middle MOF-on-MOF growth involving self-structural adjustment of the secondary MOF, logical inference of unidentified MOF structures based on MOF-on-MOF growth behavior and morphological features, and MOF-on-MOF growth accompanied by etching and transformation of the template. Finally, we discuss the perspectives and challenges of MOF-on-MOF growth and the synthesis of naturally nonpreferred MOFs. We hope that this Account offers valuable insights into the rational design and development of MOFs with desired structural and compositional characteristics, leading to the creation of ideal MOFs.

中文翻译：

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MOF-on-MOF 生长：诱导自然非首选 MOF 和非典型 MOF 生长


溢出的金属有机框架 （MOF） 已由各种金属和有机成分合成，用于特定目的和求知欲。每种 MOF 都具有独特的化学和结构特征，由掺入的组分、金属离子（或簇）、有机接头及其内在的配位相互作用指导。这些掺入的成分和结构特性是影响 MOF 基本特性和后续应用的两个关键因素。因此，考虑到其固有的化学和结构特性，选择合适的金属和有机成分对于赋予最终的 MOF 所需的特性至关重要。归根结底，使用理想组件生产具有所需结构的 MOF 是实现为特定用途量身定制且具有所需特性的最佳 MOF 的最佳方法。然而，从所选组件获得具有预期结构的 MOF 仍然不成熟。在许多情况下，所得的 MOF 结构受所选组分的热力学和/或动力学优选构型（指自然优选结构）和给定反应条件的约束。此外，生产具有复杂成分、结构和形态的杂化 MOF 为获得具有先进性能和功能的特殊 MOF 提供了绝佳的机会。在本账户中，我们概述了我们小组在过去几年中通过诱导的 MOF-on-MOF 生长过程开发天然非首选 MOF 的努力，以及通过非标准 MOF-on-MOF 生长开发非典型杂交 MOFs。首先，我们强调了基于模板诱导的 MOF-on-MOF 生长产生天然非首选 MOF 的主要策略。 在本节中，我们讨论了两种基本的生长行为，即天然非首选 MOF 的各向同性和各向异性生长，由两种 MOF 的细胞晶格之间的匹配程度决定。其次，我们引入了 MOF 农业概念，用于生产性栽培和有效收获由 MOF-on-MOF 生长产生的天然非首选 MOF。在这里，我们讨论了选择理想的 MOF 模板以实现生产性生长和开发收获栽培 MOF 的有效方法的重要性。接下来，我们描述了两个具有错配细胞晶格的 MOF 之间的非典型各向异性 MOF-on-MOF 生长。在本节中，我们介绍了从尖端到中间的 MOF-on-MOF 生长，涉及次级 MOF 的自结构调整，基于 MOF-on-MOF 生长行为和形态特征的未识别 MOF 结构的逻辑推断，以及 MOF-on-MOF 生长伴随着模板的蚀刻和转换。最后，我们讨论了 MOF-on-MOF 生长和天然非首选 MOF 合成的前景和挑战。我们希望这个账户能为合理设计和开发具有所需结构和组成特征的 MOF 提供有价值的见解，从而创造理想的 MOF。