Discotic liquid crystals of transition metal complexes. Part 32. Synthesis and liquid-crystalline properties of doubledeckers and tripledeckers based on cerium complexes of bis- and tetrakis(3,4-dialkoxyphenyl)porphyrin
Discotic liquid crystals of transition metal complexes. Part 32. Synthesis and liquid-crystalline properties of doubledeckers and tripledeckers based on cerium complexes of bis- and tetrakis(3,4-dialkoxyphenyl)porphyrin
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DOI：
10.1039/b109998c
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发表时间：
2002-03
影响因子：
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通讯作者：
T. Nakai;K. Ban;K. Ohta;M. Kimura
中科院分区：
文献类型：
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作者：
T. Nakai;K. Ban;K. Ohta;M. Kimura
Bis[5，15-bis(3，4-dialkoxyphenyl)porphyrinato]cerium(IV)(2：[(CNO)4BPP]2Ce；n=14)，bis[5，10，15，20-tetrakis(3，4-dialkoxyphenyl)porphyrinato]cerium(IV)(5：[(CNO)8TPP]2Ce；n=8，10，12，14，16，18)和tris[5，10，15，20-tetrakis(3，4-dialkoxyphenyl)porphyrinato]cerium(IV)(6：[(CNO)8TPP]3Ce2；5，15-二(3，4-二烷氧基苯基)卟啉(1：(CNO)4BPPH2)和5，10，15，20-tetrakis[3，4-bis(octadecyloxy)phenyl]porphyrins(4：(CNO)8TPPH2)。通过显微镜观察、DSC测量和随温度变化的X射线衍射研究，详细地表征了所有夹心型Ce3+配合物的中间相结构。我们研究了从片状中间相显示的卟啉到柱状中间相显示的卟啉的临界分子结构的变化。我们发现，当中心核被十二个以上的烷氧基链取代时，这些夹心型多层分子可能会呈现柱状中间相。
Novel sandwich-type doubledecker and tripledecker cerium complexes, bis[5,15-bis(3,4-dialkoxyphenyl)porphyrinato]cerium(IV) (2: [(CnO)4BPP]2Ce; n = 14), bis[5,10,15,20-tetrakis(3,4-dialkoxyphenyl)porphyrinato]cerium(IV) (5: [(CnO)8TPP]2Ce; n = 8,10,12,14,16,18), and tris[5,10,15,20-tetrakis(3,4-dialkoxyphenyl)porphyrinato]cerium(IV) (6: [(CnO)8TPP]3Ce2; n = 10), have been synthesized by using the corresponding metal free derivatives, 5,15-bis(3,4-dialkoxyphenyl)porphyrin (1: (CnO)4BPPH2) and 5,10,15,20-tetrakis[3,4-bis(octadecyloxy)phenyl]porphyrins (4: (CnO)8TPPH2) which were previously reported to show a discotic lamellar(DL) mesophase. The mesophase structures of all these sandwich-type cerium complexes have been characterized in detail by microscopic observation, DSC measurements and temperature-dependent X-ray diffraction studies. We have investigated the critical molecular structure changing from lamellar mesophase-showing porphyrins to columnar mesophase-showing ones. We found that these sandwich-type multideckers may exhibit a columnar mesophase, when the central core is substituted by more than twelve alkoxy chains.