Molecular and spin dynamics in dimetallofullerenes with single-electron metal-metal bond

双金属富勒烯中稀土金属之间的单电子金属-金属键的稳定化导致具有不寻常自旋性质的空气稳定顺磁分子。巨大的超精细耦合和定义明确的电子-核自旋能级系统在这些分子中结合在一起，将自旋限制在保护碳笼内，这使得它在化学上稳定，但能够用外部刺激寻址和操纵自旋状态。这种性质的组合开辟了一条道路，实现这种富勒烯分子在超分子结构和自旋电子器件与量子计算，自旋极化运输或磁场传感的潜在应用。这些应用将需要改进的控制的静态和动态自旋性质的dimetallofullerenes，如g和超精细张量，自旋晶格和自旋自旋弛豫时间，和退相干机制。分子结构的可变性和富勒烯内部金属原子的动力学也对自旋性质有很大影响。在这个项目中，莱布尼茨固态和材料研究所的专业知识（IFW Dresden）在内嵌金属富勒烯及其衍生物的合成和表征方面以及Zavoisky物理技术研究所的熟练程度（KPhTI喀山，科学联邦研究中心«俄罗斯科学院喀山科学中心»的分部）在先进的连续-波和脉冲EPR的研究和自旋操纵分子材料将结合起来，以发展一个基本的理解与单电子金属-金属键的双金属富勒烯分子和自旋动力学之间的关系。为了实现这一目标，IFW Dresden将优化此类二金属富勒烯的合成和分离，并制备一系列具有不同金属及其组合、各种富勒烯笼和各种外嵌体功能化的新化合物。KPhTI Kazan将通过连续波和脉冲EPR方法在不同温度，波段以及不同环境和基质中对这些化合物的自旋性质进行详细研究。对两个研究小组获得的结构和光谱数据进行综合分析，将建立分子结构、静态自旋参数、分子动力学、自旋动力学和退相干机制之间的相关性。

Stabilization of single-electron metal–metal bond between rare-earth metals in dimetallofullerenes results in air stable paramagnetic molecules with unusual spin properties. Giant hyperfine coupling and a system of well-defined electron-nuclear spin levels are combined in these molecules with confinement of the spin within the protecting carbon cage, which makes it stable chemically but enables addressing and manipulation of the spin states with external stimuli. This combination of properties opens a way to implementation of such fullerene molecules in supramolecular architectures and spintronic devices with potential applications for quantum computing, spin polarized transport or magnetic field sensing. These applications will require improved control of the static and dynamic spin properties of dimetallofullerenes, such as g and hyperfine tensors, spin-lattice and spin-spin relaxation times, and decoherence mechanisms. Variability of the molecular structure and dynamics of metal atoms inside the fullerene also have a strong impact on the spin properties. In this project, the expertise of Leibniz Institute for Solid State and Materials Research (IFW Dresden) in the synthesis and characterization of endohedral metallofullerenes and their derivatives and the proficiency of Zavoisky Physical-Technical Institute (KPhTI Kazan, Subdivision of Science Federal Research Center «Kazan Scientific Center of Russian Academy of Sciences») in advanced continuous-wave and pulsed EPR studies and spin manipulation in molecular materials will be combined to develop a fundamental understanding of the relation between molecular and spin dynamics in dimetallofullerenes with single-electron metal-metal bonds. Toward this goal, IFW Dresden will optimize the synthesis and separation of such dimetallofullerenes and prepare an array of new compounds featuring different metals and their combinations, various fullerene cages, and diverse exohedral functionalizations. KPhTI Kazan will perform detailed study of the spin properties of these compounds by continuous wave and pulsed EPR methods at different temperatures, bands, and in different environments and matrices. Comprehensive analysis of the structural and spectroscopic data obtained by both groups will establish correlations between the molecular structure, static spin parameters, molecular dynamics, and spin dynamics and decoherence mechanisms.