ET类正组元导电分子晶体及相关负离子工程

【作者】 陈红余；

【导师】 方奇； 于文涛；

【作者基本信息】 山东大学 ， 材料学， 2006， 博士

【摘要】 在过去的几十年里，对于更高超导转变温度超导体的探索研究一直是一个相当活跃的领域。其中对于电荷转移盐类有机金属和有机超导体的研究备受关注。基于电子给体BEDT-TTF的正组元分子导体又是其中成果最丰富的一支。 本论文主要进行了ET类正组元导电分子晶体及相关负离子的探索，首次结构表征了16种新晶体的结构，其中设计合成并结构表征了5个新的ET正组元导电分子晶体，研究了其结构，电性质以及二者之间的关系。论文立足负离子设计的角度，引入五方酸负离子作为平衡离子参与ET类导电分子晶体的架构，系统地研究了五方酸类化合物的结构化学行为。本文的工作主要包括： 一是利用不同类型负离子与ET分子进行导电分子晶体架构，探讨了ET类正组元导电分子晶体的生长技术；通过对获得的新晶体的结构与变温电导的测试，研究了其导电行为与结构之间的关系。 1．利用不同类型的负离子与ET进行电化学结晶，得到了5种新的ET正组元导电分子晶体，并完成了详细的结构表征。我们在晶体的生长试验中发现，导电分子晶体本身及其组成负离子的物理化学性质对最终得到晶体的质量有着较大的影响。高对称性负离子较容易架构出高质量的晶体。而晶体生长的各组分在有机电解液中的输运效率对晶体的结构和质量有着非常重要的影响。电导率较高的晶体容易生长得到高质量的晶体。同时本论文通过结构分析和光谱手段，确定了新晶体中给体分子的氧化态。更多还原

【Abstract】 In the last 40 years, scientists have been actively engaged in developing high temperature superconductors. Extensive works have been carried out in the design of organic conductors of charge-transfer complexes based on planar π-molecules, which can be donors or acceptors or both. Mostly obtained organic conductors and superconductor structures are based on BEDT-TTF ( Bis(ethylenedithio)tetrathiafulvalene, abbreviated as ET).BEDT-TTFThis article mainly deals with crystal growth of ET-based molecular conductors and relative anions. There are 16 new kinds of crystals being obtained and their structure have been determined by X-ray method. Five kinds of ET-based molecular conductors have been synthesized and their crystal structures and properties have been systematically studied. As our contribution to explore ET-based molecular conductor on anion engineering, we first introduce the croconate anions as counterions. The structure chemistry of the croconate has been systematically studied. The important contents and conclusion are as following:The first section: ET-based molecular conductors with various balance anions have been electrocrystallized and their crystal structures have been determined. Crystal growth, crystal structures, conducting properties and the structure-property relationships between those compounds are systematically studies.1. Five new kinds of ET-based molecular conductors with various balance anions have been electrocrystallized and their structures have been determined by X-ray method. In our research, we found that there are three intrinsic factors that determine the crystal quality, (i) High symmetry anions are easily to form single crystal of high quality among molecular conductors, (ii) Mass transfer in the electrolyte has great effect on the structure and the quality of the obtained crystal, (iii) Generally, molecular conductor based on BEDT-TTF is often grown in the direction of high conductivity. So high conductivity molecular conductor is easily to get high quality single crystal. And we also determined the oxidative state of BEDT-TTF in the obtained molecular conductors through bond lengths analysis and Raman spectra.更多还原