将前体物5,6-二氰基-2-(4’,5’-二硫-(3’,6’,9’ -三氧十一烷基)-1,3-二硫-2-叶立德)-苯并-1,3-二硫(化合物1)直接环四聚化合成了4个冠醚环化的TTF结构单元以共轭的形式直接与酞菁相连的无金属酞菁化合物2,9,16,23-四[4’,5’-二硫-(3’,6’,9’ -三氧十一烷基)四硫富瓦烯]酞菁(化合物2),对二者进行了元素分析和IR、UV、MS等表征。解析了化合物1的晶体结构,并对二者的电化学行为作了初步的分析。结果表明,化合物1的大环部分和其他单冠醚的化合物类似,也为冠状构型,有利于金属的配位,而质谱上位于2109处的分子离子峰以及红外光谱中3423 cm-1和1070 cm-1处酞菁中N-H的伸缩振动和弯曲振动则证明了化合物2的存在。化合物1和化合物2对Li+均有较好的络合选择性(氧化还原电对向正方向移动),表明它们有可能成为新的氧化还原传感器。
Abstract
A metal-free, a-(crown-ether-tetrathiafulvalene) annulated phthalocyanine 2 (2, 9, 16, 23-tetrakis[4’,5’-dithia-(3’,6’,9’–trioxaundecyl)tetrathiafulvalene]phthalocyanine) was synthesized by tetramerization of the corresponding phthalonitrile precursor 1 (5, 6-dicyano-2-(4’,5’-dithia-(3’,6’,9’-trioxaundecyl)-1, 3-dithio-2-ylidene)-benzo-1, 3-dithiole). We characterized them by elemental analysis, IR, UV, and MS spectra. The crystal structure of the precursor and their electrochemical properties were analyzed. The results indicate that the macrocycle in 1 adopts a crown conformation, which is in favor of metal complexation as some other monocrown compounds. The presence of the characteristic molecular ion peak at m/z = 2109 [M]+ in the mass spectrum and the resonances at 3423 cm-1 and 1070 cm-1 assigned to the N-H stretching and bending vibrations support the proposed structure of 2. 1 and 2 have good complexation selectivity for Li+ with large positive redox shifts, indicating that they may be a new redox-active sensor.
关键词
冠醚 /
TTF /
酞菁 /
晶体结构 /
电化学性质
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Key words
Crown-ether /
TTF /
phthalocyanine /
crystal structure /
electrochemical property
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参考文献
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脚注
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基金
中央高校基本科研业务费专项资金资助项目(DC13010306);大连民族大学人才启动基金资助项目(0701-110080)。
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