3d-4f混金属纳米分子磁体的设计, 合成及磁构关系研究

Molecular nanomagnets have recently becoming one of the most intense interests of the chemistry, physics, and material science due to their potential applications in ultrahigh-density information storage, quantum computing, and molecular spintronic devices. In order to reveal the magnetostructural correlations and to fine-tune the magnetic properties, in this project, a series of 3d-4f heterometallic complexes with zero- and one-dimensional motifs will be synthesized by the self-assembly reations of mixed heterobridges (azolate-carboxylate, oximate-carboxylate, nucleobase-carboxylate and so on) with paramagnetic 3d and 4f metal ions, their crystalline structures, static and dynamic magnetic properties, as well as theoretical computations will be carried out in more details. The significant influences of the various factors (such as mixed heterobridges, heterometallic effect, ligand-field effect, topology effect of the spin carriers, and so on) on the geometric parameters, electronic structure, and magnetic orbital energy level will be fully discussed based on the combined experimental and theoretical results. All these important findings would greatly advance the understanding of the magnetostructural correlations, provide skillful experience for the bulky preparations, accelerate the development of the 3d-4f heteronuclear molecular nanomagnets and push the practicalization process of the molecule-based magnets.

纳米分子磁体因在高密度信息储存器件、量子化学计算以及分子自旋电子学等领域具有潜在的应用前景而成为化学、物理学和材料学等众多学科的前沿交叉研究领域之一。申请立项以3d-4f混金属纳米分子磁体磁构关系的揭示和磁学性能调控为主要目标，围绕唑基-羧基、肟基-羧基、核酸碱基-羧基等混合磁桥合成多个系列的3d-4f混金属混桥的零维或一维金属配合物，并对其进行全面的固态晶体结构表征、静态和动态磁学性能测试以及量子化学理论计算。从实验表征和理论计算结果相结合的角度深入考查混合磁桥、杂原子效应、配位体场效应、自旋载体拓扑结构等多种因素对混金属纳米分子磁体几何结构、电子结构以及磁轨道能级的影响规律，进而全面地诠释3d-4f混金属纳米分子磁体的磁构关系，为实现高性能、可应用的纳米分子磁体的宏量制备提供技术经验和理论支撑，促进纳米分子磁体研究领域的发展，推动分子基磁体的实用化进程。

纳米分子磁体因在高密度信息储存器件、量子化学计算以及分子自旋电子学等多领域诱人的应用前景而成为化学、物理学和材料学等众多学科的交叉研究内容之一。项目以3d-4f混金属纳米分子磁体磁构关系的认识和磁学性能的调控为主要目标，围绕联吡啶基-羧基、肟基-羧基、酚羟基-羧基以及多唑基-羧基等混合短桥设计并合成了多个系列的{DyIIINiII}、{DyIIIZnII}、{DyIIIMnII}、{DyIIICuII}、{TbIIINiII}、{GdIIINiII}等双核至十八核的零维分子簇和一维金属配合物，并对其晶体结构、组分热稳定性、晶相纯度、静态和动态磁学性能的测试以及量子化学理论计算等开展了研究。结合实验表征和理论计算结果探讨了混金属配合物的制备方法、混合磁桥组合、自旋载体配位几何、配位体场效应、自旋载体拓扑结构等因素对混金属单分子磁体的几何结构、电子结构以及磁轨道能级的影响规律，较为全面地阐述了这些混桥混金属纳米分子磁体的磁构关系，为高性能、可应用的纳米分子磁体的宏量制备积累了技术经验，发展并完善了3d-4f混金属分子磁体磁性能的影响因素，推动了纳米分子磁体磁构关系的发展。