【作者】 张萱；

【导师】 秦金贵；

【作者基本信息】 武汉大学 ， 有机化学， 2004， 硕士

【摘要】 近二十年来，有机—无机纳米复合材料由于其重要的理论研究价值和广阔的应用前景，引起学术界的广泛关注。夹层作用代表了一种设计并合成此类材料的新思路，由有机客体插入无机主体而形成的夹层化合物，可以通过主客体性质的协同或互补得到具有特殊光、电和磁性质的新型功能材料甚至是多功能材料，因而成为目前功能材料领域的研究热点之一。 本论文由三部分研究工作组成。第一部分（第二章至第四章）是研究以主体硫代亚磷酸锰（MnPS₃）与一些有机客体所形成的新型夹层化合物的合成、组成与结构鉴定及其电、磁性质，并对某些夹层反应机理进行了探讨。第二部分（第五章）是研究混合金属硫代亚磷酸盐及其夹层化合物的合成、组成与结构鉴定及其磁学性质。第三部分（第六章）则研究了以过渡金属二硫化物为主体的新型有机—无机夹层化合物的合成、结构和电、磁性质。本论文共合成了16个新化合物，包括4个层状硫代亚磷酸锰的夹层化合物，3个层状混合金属硫代亚磷酸盐，6个层状混合金属硫代亚磷酸盐的夹层化合物和3个二硫化钼的夹层化合物。 第一章综述了夹层化合物的合成、结构和性能等方面的最近研究进展及应用前景，特别是以过渡金属硫代亚磷酸盐和过渡金属二硫化物为主体的夹层化合物的研究状况，在此基础上提出了本论文工作的设计思想和研究内容。 第二章通过预夹层化合物Mn_0.83PS₃（bipy）_0.51与（TTM-TTF）I_x反应合成了一个新的夹层化合物Mn_0.83PS₃（TTM-TTF）_0.50。根据X—射线粉末衍射分析，夹层化合物Mn_0.83PS₃（TTM-TTF）_0.50的层间距扩大值约为3.5（?），由此确定客体TTM-TTF在层间采取其分子环平面平行于主体层的方式排列。由红外光谱发现在夹层化合物Mn_0.83PS₃（TTM-TTF）_0.50中，客体TTM-TTF在层间以中性和阳离子两种状态存在，其电导率值约为4.0×10^-7S／cm，比纯主体MnPS₃的室温电导率(＜10^-10 S／cm)略好但并无很大提高，这与客体TTM-TTF在主体层间的排列方式及存在形式一致。研究了夹层化合物Mn_0.83PS₃（TTM-TTF）_0.50的磁学性质，可以发现夹层化合物在低温阶区出现了三个阶段的磁相变。在40 K左右，发生了一个较弱的亚铁磁相变，但是在30 K以下又变为反铁磁相互偶合作用占主导作用。然而在5 K左右出现自发磁化，呈现比较明显的亚铁磁相变。 第三章合成了一系列新夹层化合物[Fe（Salen）]_0.56Mn_0.72PS₃·0.5H₂O，[Mn（Salen）]_0.26Mn_0.87PS₃·0.5H₂O和[Co（Salen）]_0.70Mn_0.65PS₃·H₂O。通过X—射线粉末衍射、红外光谱、元素分析和热分析对该系列夹层化合物的结构组成进行了鉴定，并对客体排列方式进行了探讨。根据该系列夹层化合物的层间距变化，推断在夹层化合物[Fe（Salen）]_0.56Mn_0.72PS₃·0.5H₂O和[Mn（Salen）]_0.26Mn_0.87PS₃·0.5H₂O中（层间距变化约为9-10（?）），客体在层间以其分子平面二重轴垂直于主体层的方向排列；而在夹层化合物[Co（Salen）]_0.70Mn_0.65PS₃·H₂O（层间距变化为14（?）），客体分子在层间的排列可能是其平面长二轴在垂直于主体层平面的方向上有一小角度的倾斜。用SQUID对夹层化合物的磁性进行了测定，其中夹层化合物[Fe（Salen）]。56Mn072PS3·0.5H2O和[Mn（Salen）]o26Mno名7PS3·0.5H2O均在约40K以下出现自发的磁化现象，显示出宏观亚铁磁性;而夹层化合物【Co（s alen）107oMnD65Ps3·HZO则为顺磁性。上述三个夹层化合物在测试温度范围内均没有出现明显的自旋交叉效应。 第四章通过X一射线粉末衍射法追踪，对2，2’一联毗咤与层状硫代亚磷酸锰（MnPSs）夹层反应机理进行了研究，证实了一种奇特的夹层反应新现象—原位配位夹层作用，这种现象在夹层化学中十分罕见。实验中我们发现酸的存在与否对于夹层反应过程及其客体的存在方式有很大影响。在A系列实验中，反应体系内有四相共存:口01相为纯主体;O0l’相代表2，2’一联毗睫平面平行于主体层排列;001”相则代表其分子平面二次轴垂直于主体层排列，这一相只是口01川相形成的一个中间过渡相;口01，，，相则代表客体阳离子「Mn（biPy）3]2+，它源于主体MnPS3层内掉下来的Mn2+与插入层间的客体（中性的2，2’一联毗陡）在层间的原位配位。随着反应时间的推移，口01，口01’和001”相的衍射峰强度渐渐变弱并最终消失，而001”，相的强度则逐渐增强，最后形成仅含口01’”相的夹层化合物困o.AS)。在B系列实验中，由于酸的存在，使得[Mn（biPy）s]2+的形成被抑制。而且酸的用量的多少成为影响客体存在形式的关键因素。随着酸用量的增加，质子化的2，2’一联毗咤成为体系中客体的主要存在方式，并且分子平面二次轴垂直于主体层排列。C系列实验的结果则是对A和B系列实验的一个很好的补充。根据实验的结果，我们提出了在不同条件下的2，2’一联毗咤与MnPS3夹层反应的可能反应机理，并阐明了阳离子【Mn（b ipy）3〕2+在主体层间的原位形成过程。 第五章通过高温固相合成法制备了一系列过渡金属硫代亚磷酸盐MnxCdl.xPS3（0<X夕）14，并合成了两个系列的相应夹层化合物MnxCdl_xPS3一E叨（A1一4）和MnxCdl一xPS更多还原

【Abstract】 In recent years much attention has been drawn to inorganic-organic nanocomposite materials due to their promising applications in many fields. Intercalation of organic species into layered inorganic solids represents one of the useful approaches to design and synthesize some functional and multifunctional materials including optical, electric and magnetic materials.The thesis contains three parts of the research work. The first part (Chapters 2-4) mainly describes the synthesis, structural characterization and properties of some new intercalation compounds based on the host MnPS3. The second part (Chapter 5) describes the synthesis, structural characterization and magnetic properties of a new series of mixed transition metal phosphorus sulfides MnxCd1-xPS3 and two series of intercalates based on these hosts. The third part (Chapter 6) studies the synthesis, structural characterization and magnetic, electrical properties of a series of intercalates based on MoS2. In this thesis, sixteen new compounds have been synthesized including four intercalation compounds of the lamellar MnPS3, three mixed transition metal phosphorus sulfides MnxCd1-xPS3 and six intercalates based on these hosts, and three intercalates based onChapter 1 reviews the recent advances on the intercalation compounds and their promising applications in many fields,especially about the synthetic methods,structures, properties and potential applications of the intercalates based on layered MPS3 and transition metaldichalcogenides. Furthermore,the design strategies and the contents of the thesis are outlined in this chapter.Chapter 2 describes the synthesis, structural characterization and some solid-state physical properties of a new intercalation compound of TTM-TTF (tetrathiomethyl tetrathiafulvalene) into MnPS3, which was obtained by treating the pre-intercalate Mn0.83PS3(bipy)0.51with (TTM-TTF)Ix in acetonitrile. Compared with pure MnPS3, the lattice spacing is increased by about 3.5 A, which means that the molecular ring plane of the guest is almost parallel to the layer of the host. From the IR spectra, it can be seen that the intercalate exhibits the characteristic absorptions of both neutral TTM-TTF and cationic TTM-TTF. The room-temperature electrical conductivity of the compressed pellet of Mn0.83PS3(bipy)0.51 is around 4.0x 10-7 S/cm, which is a little bettsr than that of the pristine MnPS3. Its magnetic property is studied with SQUID. Three magnetic transitional periods occur in the range between 40 K and 5 K. The first magnetic transition at 40 K indicates a weak ferromagnetic transition, but in the range of 30 K to 5 K, the antiferromagnetism plays the main role in it. And anothermagnetic transition at 5 K indicates that the new intercalate exhibits bulk spontaneous magnetism below 5 K.In Chapter 3, a new series of intercalation compounds, in which a series of cationic complexes [M(Salen)]+ (M = Mn, Fe, Co) are intercalated into the lamellar MnPS3, have been synthesized. Compared with MnPS3, the lattice expansion (Ad) of 9-10 A for [Fe(Salen)]0.56Mno.72PS3-0.5H2O and [Mn(Salen)]0.26Mn0.87PS3-0.5H2O, indicates that the molecular ring of the guest is perpendicular to the layer of the host. While the lattice expansion (Ad) of 14 A for [Co(Salen)]0.7oMno.65PS3-H2O, suggests that the molecular ring of the guest has a tilted angle between the layer of the host. The results of SQUID measurements of [Fe(Salen)]o.56Mno.72PS3-0.5H2O and [Mn(Salen)]0.26Mno.87PS3-0.5H2O indicate they show bulk spontaneous magnetization below 40 K, while intercalate [Co(Salen)]o.7oMno.65PS3’H2O exhibits paramagnetism. In the whole temperature range of the measurement, no spin crossover behavior is observed for this series of intercalates.In Chapter 4, the intercalation process of 2,2’-bipyridine into layered MnPS3 is studied with powder XRD technology in detail. From the XRD results it is found that the absence or presence of acid greatly influences the existing form and the arranged orientation of the guest. In Series A, only MnPS3 and 2,2’-bipyridi更多还原