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Carborane Meets Metal Nanocluster: New Opportunities in Nanomaterials
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2025-03-28 , DOI: 10.1021/acs.accounts.5c00033
Jia-Hong Huang 1 , Yao Cui 1 , Zhao-Yang Wang 1 , Shuang-Quan Zang 1
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2025-03-28 , DOI: 10.1021/acs.accounts.5c00033
Jia-Hong Huang 1 , Yao Cui 1 , Zhao-Yang Wang 1 , Shuang-Quan Zang 1
Affiliation
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Metal nanoclusters, distinguished by their atom-precise structures and quantum size effect, are regarded as a crucial bridge between organometallic complexes and plasmonic metal nanoparticles. These nanoclusters are primarily composed of a metallic core enveloped by protective ligands, wherein the ligands play a vital role in determining the nanoclusters’ synthesis, structural integrity, and physicochemical properties. Considerable efforts in ligand engineering have concentrated on exploring novel coordinating functional groups to advance nanocluster research, particularly in the precise and controlled synthesis of superatomic nanoclusters, fine-tuning their intrinsic properties, and subsequent assembly and application. However, the backbone of these ligands seems equally important but attracts less attention. It is reasonable that if the utility of the two moieties (coordinating functional group and backbone) provokes a profound synergistic effect, their contributions to the structures and properties of the resultant metal nanoclusters are extremely inestimable. In this context, carborane, with its spherical shape and three-dimensional aromaticity (electronic effect), has emerged as a promising candidate for ligand backbone design. Over the past two decades, the incorporation of carborane moieties into ligands has enabled the construction of various metal nanoclusters exhibiting distinct architectures, enhanced stability, and unique reactivity. Therefore, it is important to present the current status and challenges associated with carboranyl ligand-protected metal nanoclusters to guide their future development. This Account provides a comprehensive summary of the recent advances in carboranyl ligand-stabilized metal nanoclusters, with a primary focus on the contributions from our laboratory. We begin by discussing the unique advantages of introducing carborane-based ligands in metal nanocluster preparation, with particular emphasis on their virtues for the synthesis of superatomic nanoclusters, heterometal-doped nanoclusters, and isostructural nanoclusters. Subsequently, we summarize the carborane-based ligand engineering strategies for precise modification and hierarchical assembly of metal nanoclusters, elucidating how the incorporation of carborane facilitates the modulation of specific properties and promotes supramolecular and covalent assembly. Furthermore, we discuss the cooperativity achieved by carboranyl ligands and the metal nanocluster framework to broaden the scope of applications for these nanoclusters in versatile fields, including hypergolic fuels, a previously unexplored area. Finally, we discuss the challenges facing future research on carboranyl ligand-protected metal nanoclusters, including the incorporation of nido-carborane or metallocarborane, a fundamental understanding of structure–property relationships, and potential applications such as boron neutron capture therapy and radionuclide extraction. This Account aims to stimulate interest in the unique attributes of carborane-based ligands and their corresponding metal nanoclusters among students and researchers across diverse disciplines, including chemistry, crystal engineering, and materials science.
中文翻译：
碳硼烷遇见金属纳米团簇：纳米材料的新机遇
金属纳米团簇以其原子精确结构和量子尺寸效应而著称，被认为是有机金属配合物和等离激元金属纳米颗粒之间的重要桥梁。这些纳米团簇主要由被保护性配体包裹的金属核心组成，其中配体在决定纳米团簇的合成、结构完整性和物理化学性质方面起着至关重要的作用。配体工程方面的大量努力集中在探索新的配位官能团以推进纳米团簇研究，特别是在超原子纳米团簇的精确和受控合成、微调其本征特性以及随后的组装和应用方面。然而，这些配体的骨架似乎同样重要，但吸引的关注较少。如果这两个部分（配位官能团和主链）的效用引发了深远的协同效应，那么它们对所得金属纳米团簇的结构和性质的贡献是极其不可估量的，这是合理的。在此背景下，碳硼烷凭借其球形和三维芳香性（电子效应），已成为配体骨架设计的有前途的候选者。在过去的二十年里，碳硼烷部分掺入配体中，使得构建各种金属纳米团簇成为可能，这些金属纳米团簇表现出不同的结构、增强的稳定性和独特的反应性。因此，介绍碳硼酰配体保护金属纳米团簇的现状和挑战以指导其未来发展非常重要。 本账户全面总结了碳硼酰配体稳定金属纳米团簇的最新进展，主要关注我们实验室的贡献。我们首先讨论了在金属纳米团簇制备中引入碳硼烷基配体的独特优势，特别强调了它们在合成超原子纳米团簇、异金属掺杂纳米团簇和等构纳米团簇方面的优点。随后，我们总结了基于碳硼烷的配体工程策略，用于金属纳米团簇的精确修饰和分层组装，阐明了碳硼烷的掺入如何促进特定特性的调节并促进超分子和共价组装。此外，我们讨论了碳硼酰配体和金属纳米团簇框架实现的协同性，以扩大这些纳米团簇在多功能领域的应用范围，包括以前未开发的高氢燃料。最后，我们讨论了碳硼酰配体保护金属纳米团簇未来研究面临的挑战，包括钴基碳硼烷或金属碳硼烷的掺入、对结构-性质关系的基本理解，以及硼中子俘获疗法和放射性核素提取等潜在应用。本账户旨在激发不同学科（包括化学、晶体工程和材料科学）的学生和研究人员对碳硼烷基配体及其相应金属纳米团簇的独特属性的兴趣。
更新日期：2025-03-28
中文翻译：
碳硼烷遇见金属纳米团簇：纳米材料的新机遇
金属纳米团簇以其原子精确结构和量子尺寸效应而著称，被认为是有机金属配合物和等离激元金属纳米颗粒之间的重要桥梁。这些纳米团簇主要由被保护性配体包裹的金属核心组成，其中配体在决定纳米团簇的合成、结构完整性和物理化学性质方面起着至关重要的作用。配体工程方面的大量努力集中在探索新的配位官能团以推进纳米团簇研究，特别是在超原子纳米团簇的精确和受控合成、微调其本征特性以及随后的组装和应用方面。然而，这些配体的骨架似乎同样重要，但吸引的关注较少。如果这两个部分（配位官能团和主链）的效用引发了深远的协同效应，那么它们对所得金属纳米团簇的结构和性质的贡献是极其不可估量的，这是合理的。在此背景下，碳硼烷凭借其球形和三维芳香性（电子效应），已成为配体骨架设计的有前途的候选者。在过去的二十年里，碳硼烷部分掺入配体中，使得构建各种金属纳米团簇成为可能，这些金属纳米团簇表现出不同的结构、增强的稳定性和独特的反应性。因此，介绍碳硼酰配体保护金属纳米团簇的现状和挑战以指导其未来发展非常重要。 本账户全面总结了碳硼酰配体稳定金属纳米团簇的最新进展，主要关注我们实验室的贡献。我们首先讨论了在金属纳米团簇制备中引入碳硼烷基配体的独特优势，特别强调了它们在合成超原子纳米团簇、异金属掺杂纳米团簇和等构纳米团簇方面的优点。随后，我们总结了基于碳硼烷的配体工程策略，用于金属纳米团簇的精确修饰和分层组装，阐明了碳硼烷的掺入如何促进特定特性的调节并促进超分子和共价组装。此外，我们讨论了碳硼酰配体和金属纳米团簇框架实现的协同性，以扩大这些纳米团簇在多功能领域的应用范围，包括以前未开发的高氢燃料。最后，我们讨论了碳硼酰配体保护金属纳米团簇未来研究面临的挑战，包括钴基碳硼烷或金属碳硼烷的掺入、对结构-性质关系的基本理解，以及硼中子俘获疗法和放射性核素提取等潜在应用。本账户旨在激发不同学科（包括化学、晶体工程和材料科学）的学生和研究人员对碳硼烷基配体及其相应金属纳米团簇的独特属性的兴趣。
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