Single-molecule magnetism in lanthanide organometallics

具有磁性记忆的分子被称为单分子磁体（SMM）。就其尺寸和组成而言，SMM具有几纳米的尺寸，并且它们由一个或多个金属原子与一组称为配体的非金属原子键合组成。相邻分子之间的相互作用非常弱，这意味着SMM的磁性真正产生于单个分子内部。与SMM形成鲜明对比的是，日常电器中使用的传统“条形”磁铁是纯无机材料，如金属氧化物或简单的磁性元素。其应用的一个特别重要的例子是在计算机硬盘驱动器。就其尺寸和成分而言，传统磁体的磁畴要比分子大得多。由于SMM和传统磁体之间的主要差异之一与尺寸有关，因此SMM可能代表了磁信息存储的最终尺寸限制。SMM的特性可能有一天会允许它们被开发用于量子计算机。然而，SMM的一个问题是，它们的磁存储器在大约-250 ° C的温度下工作，这只能通过用液氦冷却来达到，因此是不切实际的。此外，SMM放松其磁化（即磁信息丢失或“擦除”）的机制尚不清楚，但很可能获得这些过程的理解将导致在更高的temperature.We提高性能提出了一个新的家庭的SMM的基础上镧系元素（Ln-SMM）。镧系元素为开发SMM提供了相当大的潜力，因为这些元素具有特别吸引人的磁性。最终，我们的Ln-SMM将在-196 ℃以上具有可观察到的磁记忆效应，这将是一个重大的进步，因为这个温度可以通过液氮冷却来达到，液氮是一种比液氦便宜得多的冷冻剂，更容易使用。我们将通过使用合成化学家可用的分子设计工具来实现我们的目标：我们可以对我们的配体与我们选择的镧系元素相互作用的方式进行重大改变。这一点很重要，因为用于与镧系元素相互作用的非金属原子，以及配体围绕镧系元素排列的对称性，使我们能够影响磁性。我们设计Ln-SMM方法的一个独特之处在于，我们的合成方法可以进入极其广泛的化学环境。现有的常规Ln-SMM几乎完全限于其中氧或氮与镧系元素相互作用的配体，然而我们可以使用碳、氧、硫、硒、碲、氮、磷、砷来影响磁性，锑或卤素。通过了解不同化学环境影响分子磁性的方式，我们将能够确定产生Ln的最佳条件。在前所未有的高温下工作的SMM。

Molecules that have a magnetic memory are called single-molecule magnets (SMMs). In terms of their size and composition, SMMs have dimensions of a few nanometres and they consist of one or more metal atoms bonded to a group of non-metal atoms called a ligand. The interactions between neighbouring molecules are very weak, meaning that the magnetic properties of an SMM genuinely arise from within individual molecules.In stark contrast to SMMs, traditional 'bar' magnets used in everyday appliances are purely inorganic materials such as metal oxides or simply magnetic elements. A particularly important example of their application is in computer hard disk drives. In terms of their size and composition, rather than consisting of molecules traditional magnets feature much larger magnetic domains.Because one of the main differences between SMMs and traditional magnets relates to size, it is possible that SMMs represent the ultimate size limit for magnetic information storage. The properties of SMMs may one day allow them to be developed for use in quantum computers. A problem with SMMs is, however, that their magnetic memories function at temperatures of about -250oC, which can only be reached by cooling with liquid helium and is therefore impractical. Furthermore, the mechanisms by which SMMs relax their magnetization (i.e. the magnetic information is lost or 'wiped') are not clear, but it is likely that gaining an understanding of these processes will lead to enhanced performance at higher temperatures.We propose a new family of SMMs based on the lanthanide elements (Ln-SMMs). The lanthanides offer considerable potential for developing SMMs because these elements have particularly appealing magnetic properties. Ultimately, our Ln-SMMs will have magnetic memory effects observable above -196oC, which will be a major advance because this temperature can be reached by cooling with liquid nitrogen, a cryogen that is much cheaper than liquid helium, and easier to use.We will achieve our aims by using a molecular design tool available to us as synthetic chemists: we can make significant changes to the ways in which our ligands interact with our choice of lanthanide. This is important because the non-metal atoms used to interact with the lanthanides, and the symmetry with which the ligands are arranged around the lanthanides, allow us to influence the magnetism.A unique aspect of our approach to the design of Ln-SMMs is that our synthetic method gives access to an extremely broad range of chemical environments. Existing, conventional Ln-SMMs are almost entirely limited to ligands in which oxygen or nitrogen interacts with the lanthanide, however we can influence the magnetism using carbon, oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony or the halogens.By understanding the ways in which the different chemical environments influence the molecular magnetism we will be able to identify the optimum conditions for producing Ln-SMMs that function at unprecedentedly high temperatures.