权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

The Rational Design and Preparation of Cyanometalate-Based Single-Molecule Magnets

氰基金属盐基单分子磁体的合理设计与制备

基本信息

批准号：
166831430
负责人：
Professor Dr. Peter Comba
金额：
--
依托单位：
Anorganisch-Chemisches Institut
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2010
资助国家：
德国
起止时间：
2009-12-31 至 2013-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/166831430?language=en
关键词：
Rational Design Preparation Cyanometalate Based

项目摘要

The aim of the proposal is to combine the synthesis of novel single-molecule magnetic materials (SMMs) and their detailed characterization with the accurate prediction of the corresponding molecular and crystal structures, based on molecular modeling approaches, and with quantum-chemical methods, which will allow to reliably computing the crucial electronic parameters of SMMs on the basis of the optimized structures. This novel combined approach for a rational design of SMMs, followed by their preparation and characterization, is in sharp contrast to the usual serendipity-based developments in this area, and it relies on our long tradition to combine high-level theory with empirical modeling and experimental work. It is hoped that it will allow us to produce novel tailor-made materials for applications such as high density magnetic information storage. This project follows our earlier work on the detailed analysis of the electronic properties of a series of hexacyanometalate-based oligonuclear complexes with a combination of ligand field and DFT methods, and involving a vector coupling approach to thoroughly study larger systems. The experimental work was based on hexacyanometalates of Cr3+, Fe3+, Mn3+ and Co3+, which were used to form linear and bent cyano-bridged trinuclear complexes with the mononuclear [NiII(L)]2+ and [CuII(L)]2+ complexes (L is a penta- or tetradentate bispidine ligand) as terminal fragments. The preliminary theoretical studies have resulted in a set of rules for the synthesis of novel SMMs, and these have largely been confirmed by the experimental data. However, it became clear that subtle distortions of the complex geometries generally lead to a reduction of the magnetic anisotropy and a decrease of the blocking temperature. Therefore, there is a need to accurately predict the structural properties and, apart from the experimental work, this is one of the focal points of the present grant proposal.

该提案的目的是将新型单分子磁性材料（SMM）的合成及其详细表征与相应分子和晶体结构的准确预测相结合，基于分子建模方法和量子化学方法，这将允许可靠地计算SMM的关键电子参数优化结构的基础上。这种新颖的组合方法的合理设计的SMM，其次是他们的准备和表征，是在这一领域的发展形成鲜明对比，通常的偶然性为基础的，它依赖于我们的悠久传统，结合联合收割机高层次的理论与经验建模和实验工作。希望它能让我们生产出新型的定制材料，用于高密度磁信息存储等应用。该项目遵循我们早期的工作，详细分析了一系列基于六氰酸酯的寡聚配合物的电子性质，结合配位场和DFT方法，并涉及矢量耦合方法，以深入研究更大的系统。实验工作基于Cr ~（3+）、Fe ~（3+）、Mn ~（3+）和Co ~（3+）的六氰合物，它们与单核的[Ni Ⅱ（L）]~（2+）和[Cu Ⅱ（L）]~（2+）配合物（L是五齿或四齿的bispidine配体）形成线性和弯曲的氰基桥联三核配合物。通过初步的理论研究，提出了一套合成新型自组装分子筛的规律，这些规律在很大程度上得到了实验数据的证实。然而，很明显，复杂几何形状的细微扭曲通常会导致磁各向异性的降低和阻塞温度的降低。因此，有必要准确地预测结构特性，除了实验工作之外，这也是本拨款申请的重点之一。