论文标题:基于异杂多酸盐与有机π-电子给体的电荷转移复合物的制备及性能的研究
The Physical Properties and Synthesis of Charge Transfer Complexes Based on Organic π-electron Donors and Hetero Polyoxometalate Salts
论文作者 黄勇红
论文导师 蒋凤池；刘彩明,论文学位 硕士,论文专业 有机化学
论文单位 江西师范大学,点击次数 188,论文页数 78页File Size3200k
2003-05-01论文网 http://www.lw23.com/lunwen_1180652/ 电子受体(ET),杂多酸盐,电荷转移复合物,导电性,晶体结构
ET,plolyoxometalate salts,cation-radical salts,conductivity,crystal-structure
自从1972年发现第一个有机导体TTF-TCNQ以来，有机导体、超导体的研究引起了人们的极大兴趣。到目前为止，已发现了50多个超导体和上百个导体。随着研究的不断深入，人们发现要想通过提高维数来获得更高转变温度(T_c)的超导体从合成新的电子给体出发已经变得越来越困难和费时。而通过改变电子受体来调控π-电子给体的聚集形态也是一种获得有机导体和超导体可行方法。近年来，用杂多酸根作为对阴离子合成电荷转移复合盐备受关注。 我们主要研究了带有机官能团的Anderson型异杂多酸盐的ET的电荷转移复合盐。主要内容包括： 1、合成了两个新的带有机官能团的Anderson型异杂多酸盐[N(C_4H_9)_4)]_3[MnMo_6O_(18){(OCH_2)_3C-R}](R=NH_2、CH_2CH_3)； 2、以一系列带有机官能团的Anderson型异杂多酸盐[N(C_4H_9)_4]_3[MnMo_6O_(18){(OCH_2)_3C-R}](R=OH、NH_2、CH_2CH_3)和ET作原料通过电化学氧化还原法生长出三个新的二维结构的电荷转移复合盐晶体：1．[ET]_5{MnMo_6O_(18)[(OCH_2)_3CCH_2OH]_2}·5H_2O 2．[ET]_5{MnMo_6O_(18)[(OCH_2)_3C-CH_2CH_3]_2}·(2CH_3CN)、3．[ET]_6{MnMo_6O_(18)[(OCH_2)_3CNH_2]_2}·(2CH_2Cl_2)．并测定了它们的晶体结构，研究了1和2的导电性能，发现1从室温到20K表现出金属导电性(室温电导率σ≈470 S·cm~(-1))，2随温度变化呈半导体性质(室温电导率σ≈0.208S·cm~(-1))，其活化能为0.03eV。 3、化合物3的导电性能和三个化合物的磁性由于时间的原因来不及测试。 论文的主要创新点有： 1、化合物1、2、3是首个Anderson型(异)杂多酸盐ET的电荷转移复合盐。 2、发现通过改变Anderson型异杂多酸盐中的有机官能团不但可调控π-电子给体的聚集形态，还可得到不同电子给受体比例的电荷转移复合盐。 3、化合物3是第一个有机堆积为α’’’-相的杂多酸盐与ET的电荷转移复合物。
Huang yong hong Directed by Professor Jiang feng chi and Professor Liu cai mingOrganic conductors and superconductors have been attracted much attention since the discovery of the first organic conductor TTF-TCNQ in 1972. Up to now, hundreds of organic conductors have been synthesized, over 50 of which are superconducting. One promising way for designing high Tc superconductors is to increase the dimensionality by of organic donors. Which can be realized through not only preparing new organic donors but also changing new electron acceptors.Our research has focused on hybird molecular based on organic π-electron donors and Anderson type hetero polyoxometalate salts containing organic groups. The main work are summarized as follows:(1)Two new Anderson type heteropolyoxometalate compounds, [N(C_4H_9)_4)]_3[MnMo_6O_(18){(OCH_2)_3C-R}](R=NH_2、CH_2CH_3) , have been sucessfully synthesized.(2) Three new two-dimensional charge transfer complexes 1.[ET]_5{MnMo_6O_(18)[(OCH_2)_3CCH_2OH]_2}·5H_2O 2．[ET]_5{MnMo_6O_(18)[(OCH_2)_3C-CH_2CH_3]_2}·(2CH_3CN)、3．[ET]_6{MnMo_6O_(18)[(OCH_2)_3CNH_2]_2}·(2CH_2Cl_2)(ET-bis(ethylenedithio)-tetrathiofuvaI en) denoted as I , II, and III respectively have been Prepared by electrocyrstallization techniques. Their structure have been determined by x-ray single crystal diffraction. The conductivity measurement shows that I is metallic condutor between 20k to 300k with room temperature conductivity constant 470 S cm-1 While compound II shows semiconductor behavior, its room temperature conductivity constant is 0.0208 S cm-1 and its active energy for about 0.03 eV.(3) The conductivity property of III and the magnetic properties of I , II, and III will be measured in the near future.Main innovative points of this reseach are listed as following:(1) Complexs I , II, and III are the first examples of cation-radical salts based on Anderson type (hetero) polyoxometalate salt and ET.(2) The organic groups in Anderson type hetero polyoxometalates can induce not only new π-electron organic packing but also new stoichiometries as examplified by complexes I , II, and III.(3) Because of the a"" for organic packing of complex III, it is the first example of cation-radical salts based on polyoxometalate salt and ET .
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