Supramolecular Synthesis of Molecular Clusters: Topological Control of Hybrid Nanomagnets

顺磁性过渡金属离子多核笼子在单分子磁性和分子自旋电子学领域具有广阔的应用前景。超分子化学被定义为分子以外的化学，并研究(除其他外)分子间的相互作用。这种相互作用(例如氢键)可以对分子纳米磁体(MNM)的体相产生深远的影响，我们建议通过将这两个研究领域结合起来来调节MNM之间的相互作用。我们将通过两种不同但密切相关的方法来解决这个问题，其中包含称为杯芳烃的分子的环状空腔。这些分子可以相对容易地功能化，也可以与其他小分子结合形成共价笼状结构。为了调节这些相互作用，我们将a)在这些笼内形成金属簇合物，b)用功能杯芳烃取代MNM上的基团，以及c)用单杯芳烃或分子笼制作MNM的三维阵列。斯科特·J·达尔加诺博士在杯芳烃合成和大型超分子体系的结晶学研究方面拥有专业知识，尤安·K·布雷钦博士是分子磁学的世界领先者。这些技术将对阐明分子间相互作用的调制至关重要，并将使我们能够调整所产生的金属团簇的磁性，以便在上述应用领域进行潜在的开发。

Polynuclear cages of paramagnetic transition metal ions can exhibit fascinating physical properties and have great potential in the field of single molecule magnetism and molecular spintronics. Supramolecular chemistry is defined as chemistry beyond the molecule, and examines (amongst other things) intermolecular interactions. Such interactions (e.g. hydrogen bonding) can have profound effects on the bulk phase of molecular nanomagnets (MNM) and we propose to modulate the interactions found between MNMs by marrying the two areas of research. We are going to approach this problem in two different yet intimately related ways with cyclic cavity containing molecules called calixarenes. These molecules can be functionalised with relative ease, and can also be combined with other small molecules to make covalent cage structures. In order to modulate these interactions we will a) form metal clusters within these cages, b) substitute groups on MNMs with functional calixarenes, and c) make 3-D arrays of MNMs with single calixarenes or molecular cages. Dr. Scott J. Dalgarno has expertise in calixarene synthesis and crystallographic studies on large supramolecular systems and Dr. Euan K. Brechin is a world leader in molecular magnetism. These techniques will be critical in elucidating the modulation of the intermolecular interactions, and will allow us to tune the magnetic properties of the resulting metal clusters for potential exploitation in the aforementioned fields of application.