Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus.
Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, USA.
Chem Soc Rev. 2016 Mar 21;45(6):1597-628. doi: 10.1039/c5cs00590f.
In this review, aspects of the syntheses, structures and magnetic properties of giant 3d and 3d/4f paramagnetic metal clusters in moderate oxidation states are discussed. The term "giant clusters" is used herein to denote metal clusters with nuclearity of 30 or greater. Many synthetic strategies towards such species have been developed and are discussed in this paper. Attempts are made to categorize some of the most successful methods to giant clusters, but it will be pointed out that the characteristics of the crystal structures of such compounds including nuclearity, shape, architecture, etc. are unpredictable depending on the specific structural features of the included organic ligands, reaction conditions and other factors. The majority of the described compounds in this review are of special interest not only for their fascinating nanosized structures but also because they sometimes display interesting magnetic phenomena, such as ferromagnetic exchange interactions, large ground state spin values, single-molecule magnetism behaviour or impressively large magnetocaloric effects. In addition, they often possess the properties of both the quantum and the classical world, and thus their systematic study offers the potential for the discovery of new physical phenomena, as well as a better understanding of the existing ones. The research field of giant clusters is under continuous evolution and their intriguing structural characteristics and magnetism properties that attract the interest of synthetic Inorganic Chemists promise a brilliant future for this class of compounds.
在这篇综述中，讨论了中等氧化态下的 3d 和 3d/4f 顺磁金属巨团簇的合成、结构和磁性方面的内容。本文中使用的“巨团簇”一词是指核数为 30 或更大的金属团簇。已经开发了许多合成这些物种的策略，并在本文中进行了讨论。本文试图对一些最成功的制备巨团簇的方法进行分类，但需要指出的是，这些化合物的晶体结构特征，包括核数、形状、结构等，是不可预测的，这取决于所包含的有机配体、反应条件和其他因素的具体结构特征。本文中描述的大多数化合物不仅因其迷人的纳米结构而具有特殊的意义，而且还因为它们有时表现出有趣的磁现象，如铁磁交换相互作用、大的基态自旋值、单分子磁体行为或令人印象深刻的大磁热效应。此外，它们通常具有量子和经典世界的特性，因此对它们的系统研究有可能发现新的物理现象，并更好地理解现有的物理现象。巨团簇的研究领域在不断发展，它们引人入胜的结构特征和磁性吸引了合成无机化学家的兴趣，为这类化合物的发展带来了光明的前景。
