Discotic liquid crystals of transition metal complexes 39: columnar mesomorphism and homeotropic alignment speed of sandwich-type of double-deckers and triple-deckers based on phthalocyaninato lutetium metal complexes
Discotic liquid crystals of transition metal complexes 39: columnar mesomorphism and homeotropic alignment speed of sandwich-type of double-deckers and triple-deckers based on phthalocyaninato lutetium metal complexes
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DOI：
10.1142/s1088424607000977
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发表时间：
2007-12
影响因子：
1.5
通讯作者：
Hidetomo Mukai;Kazuaki Hatsusaka;K. Ohta
中科院分区：
文献类型：
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作者：
Hidetomo Mukai;Kazuaki Hatsusaka;K. Ohta
合成了一系列双[2，3，9，10，16，17，23，24-八（3，4-二烷氧基苯氧基）酞菁]镥（III）（{[（CnO）2 PhO] 8 Pc}2Lu（n = 8−16）：double-deckers（2））。作为副产物，三[2，3，9，10，16，17，23，24-八（3，4-二烷氧基苯氧基）酞菁]稀酞（III）（{[（CnO）2 PhO] 8 Pc} 3Lu 2（n = 8，9，11，12，14，16）：三层结构（3））被成功分离。利用偏光显微镜、差示扫描量热仪和变温X射线衍射技术研究了双层和三层介晶结构的介晶性质。对于n ≥ 10，双层（2）显示Colh、Cub和Coltet中间相。另一方面，三层结构（3）对于n = 8仅显示Colr中间相，对于n = 14仅显示Coltet中间相，并且对于n = 9、11、12和16均显示Colr和Coltet中间相。对于Coltet中间相，双层（2）和三层（3）都在大面积上表现出自发的垂面排列。与现有的镥配合物2、3和以前的铜配合物的垂面排列相比，2，3，9，10，16，17，23，24-八（3，4-二烷氧基苯氧基）酞菁铜（II）（[（CnO）2 PhO] 8 PcCu（n = 9-14）：单层（1）），排列顺序分别为快、慢、快，单层（1）、双层（2）、三层（3）。非常有趣的是，具有平坦的Pc大环的配合物1和3给出快速对齐，而具有非平坦的Pc大环的配合物2给出缓慢对齐。因此，首次揭示了无序液晶分子的平坦性影响垂面排列的速度。
A series of sandwich-type metal complexes, bis[2,3,9,10,16,17,23,24-octakis(3,4-dialkoxyphenoxy)phthalocyaninato]lutetium(III) ({[(CnO)2PhO]8Pc}2Lu (n = 8−16): double-deckers (2)), were synthesized. As the by-product, tris[2,3,9,10,16,17,23,24-octakis(3,4-diakoxyphenoxy)phthalocyaninato]dilutetium(III) ({[(CnO)2PhO]8Pc}3Lu2 (n = 8, 9, 11, 12, 14, 16): triple-deckers (3)) were successfully separated. The mesomorphic properties of these double-deckers (2) and triple-deckers (3) were investigated using a polarization microscope, differential scanning calorimetry and temperature-dependent X-ray diffraction techniques. The double-deckers (2) showed Colh, Cub and Coltet mesophases for n ≥ 10. On the other hand, the triple-deckers (3) showed only a Colr mesophase for n = 8, only a Coltet mesophase for n = 14, and both Colr and Coltet mesophases for n = 9, 11, 12 and 16. For the Coltet mesophase, both the double-deckers (2) and the triple-deckers (3) exhibited spontaneous homeotropic alignment in a large area. In comparison with the homeotropic alignment of these present lutetium complexes 2, 3 and the previous copper complexes, 2,3,9,10,16,17,23,24-octakis(3,4-dialkoxyphenoxy)phthalocyaninato copper(II) ([(CnO)2PhO]8PcCu (n = 9-14): single-decker (1)), the alignment was fast, slow and fast, respectively, in the order of the single-deckers (1), double-deckers (2) and triple-deckers (3). Very interestingly, the complexes 1 and 3 which have flat Pc macrocycles gave fast alignment, whereas the complexes, 2, which have non-flat Pc macrocycles, gave slow alignment. Thus, it was revealed for the first time that the flatness of discotic liquid crystalline molecules influences the speed of homeotropic alignment.