冠醚环化四硫富瓦烯酞菁衍生物的合成与表征

Synthesis and Characterization of Tetra-( crown-ether-tetrathiafulvalene)annulated Phthalocyanine Derivative

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1070cm-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。

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 precursor1（ 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 at3423 cm- 1and 1070 cm- 1assigned 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.