“Functional molecular systems”, discrete and self-assembled constructs where control over molecular recognition, structure, bonding, transport, release, catalytic activity, etc., is readily achieved, are a topic of current interest. Within this broad paradigm, oligopyrrolic cages have garnered attention due to their responsive recognition features. Due to the presence of slightly polar pyrrole subunits which can also behave as hydrogen-bonding donors, these oligopyrrolic cages are potential receptors for various polarized species. In this Account, we summarize recent advances involving the syntheses and study of (1) covalent oligopyrrolic macrobicyclic cages, (2) oligopyrrolic metallacages, and (3) oligopyrrolic noncovalently linked cages. Considered in concert, these molecular constructs have allowed advances in applied supramolecular chemistry; to date, they have been exploited for selective guest encapsulation studies, anion binding and ion-channel formation, and gas absorption, among other applications. While key findings from others will be noted, in this Account will focus on our own contributions to the chemistry of discrete oligopyrrolic macrocycles and their use in supramolecular host–guest chemistry and sensing applications. In terms of specifics, we will detail how oligopyrrole cages with well-defined molecular geometries permit reversible guest binding under ambient conditions and how the incorporation of pyrrole subunits within larger superstructures allows effective control over anion/conjugate acid binding activity under ambient conditions. We will also provide examples that show how derivatization of these rudimentary macrocyclic cores with various sterically congested β-substituted oligopyrroles can provide entry into more complex supramolecular architectures. In addition, we will detail how hybrid systems that include heterocycles other than pyrrole, such as pyridine and naphthyridine, can be used to create self-assembled materials that show promise as gas-absorbing materials and colorimetric reversible sensors. Studies involving oligopyrrolic polymetallic cages and oligopyrrolic supramolecular cages will also be reviewed. First, we will discuss all-carbon-linked oligopyrrolic bicycles and continue on to present systems linked via amines and imines linkages. Finally, we will summarize recent work on pyrrolic cages created through the use of metal centers or various noncovalent interactions. We hope that this Account will provide researchers with an initial foundation for understanding oligopyrrolic cage chemistry, thereby allowing for further advances in the area. It is expected that the fundamental design and recognition principles made in the area of oligopyrrole cages, as exemplified by our contributions, will be of general use to researchers targeting the design of functional molecular systems. As such, we have structured this Account so as to summarize the past while setting the stage for the future.

中文翻译：

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低聚吡咯笼：从经典分子结构到化学反应多体受体

“功能性分子系统”，即离散和自组装的结构，很容易实现对分子识别、结构、键合、运输、释放、催化活性等的控制，是当前感兴趣的话题。在这种广泛的范式中，低聚吡咯笼由于其响应识别特征而受到关注。由于存在也可以作为氢键供体的弱极性吡咯亚基，这些低聚吡咯笼是各种极化物质的潜在受体。在这个帐户中，我们总结了涉及（1）共价低聚吡咯大双环笼，（2）低聚吡咯金属笼，和（3）低聚吡咯非共价连接笼的合成和研究的最新进展。综合考虑，这些分子结构使应用超分子化学取得了进展。迄今为止，它们已被用于选择性客体封装研究、阴离子结合和离子通道形成以及气体吸收等应用。虽然将注意到其他人的主要发现，但在本报告中，我们将重点关注我们自己对离散低聚吡咯大环化学的贡献及其在超分子主客体化学和传感应用中的应用。具体而言，我们将详细介绍具有明确分子几何形状的寡聚吡咯笼如何在环境条件下实现可逆的客体结合，以及吡咯亚基如何在较大的超结构中掺入有效控制环境条件下的阴离子/共轭酸结合活性。我们还将提供示例，展示这些基本的大环核与各种空间拥挤的 β-取代低聚吡咯的衍生化如何提供进入更复杂的超分子结构的途径。此外，我们将详细介绍如何使用包含除吡咯以外的杂环（例如吡啶和萘啶）的混合系统来制造自组装材料，这些材料有望用作气体吸收材料和比色可逆传感器。还将审查涉及低聚吡咯多金属笼和低聚吡咯超分子笼的研究。首先，我们将讨论全碳连接的低聚吡咯自行车，并继续介绍通过胺和亚胺键连接的系统。最后，我们将总结最近关于通过使用金属中心或各种非共价相互作用创建的吡咯笼的工作。我们希望这个帐户将为研究人员提供了解低聚吡咯笼化学的初步基础，从而允许在该领域取得进一步进展。预计在低聚吡咯笼领域做出的基本设计和识别原则，正如我们的贡献所体现的那样，将对针对功能分子系统设计的研究人员普遍有用。因此，我们构建了这个账户，以便在总结过去的同时为未来奠定基础。预计在低聚吡咯笼领域做出的基本设计和识别原则，正如我们的贡献所体现的那样，将对针对功能分子系统设计的研究人员普遍有用。因此，我们构建了这个账户，以便在总结过去的同时为未来奠定基础。预计在低聚吡咯笼领域做出的基本设计和识别原则，正如我们的贡献所体现的那样，将对针对功能分子系统设计的研究人员普遍有用。因此，我们构建了这个账户，以便在总结过去的同时为未来奠定基础。