Synthesis and properties of ethylene-, vinylene-, and diacetylene-groups connected porphyrin hexamer

具有大面积、对外界刺激响应性强的双电子共轭环体系的寡聚化是开发新型功能有机材料的重要方法。在双电子共轭环体系中，卟啉环体系是特别有前途的，如在光合反应中心的特殊二聚体的例子中所看到的。因此，卟啉环与各种连接的低聚物已被证明可以实现各种有目的的功能，如光电流（PC）和电致发光（EL）。我们还报道了乙烯基连接的八乙基卟啉三聚体（OEP）_3的合成，并对其电子性质进行了研究，证明了其电子释放能力按（OEP）_2~（OEP）_3~（OEP）_2~（OEP）_3~（OEP）_3~（OEP）_3~（OEP）_2~（OEP）_3~（OEP）_3~（OEP）_3~（OEP）_2~（OEP）_3~（OEP）_3~（OEP）_3~（OEP）_2~（OEP）_3~（OEP）_3~（OEP）_2~（OEP）_3~（OEP）_3~（OEP）_2~（OEP）_3~（OEP）_3~（OEP）_2~（OEP）_3~（OEP）_3~（OEP）_2~（OEP）_3）_3~（OEP）_3~（OEP）_ ...更多信息 d在苹果酒中检查乙烯和乙烯基连接的OEP六聚体（OEP）6的电子性质。经过多次实验，我们成功地将甲酰基（CHO）和醇（CH_2OH）等官能团选择性地引入到（OEP）_3的中心OEP环上。并且，检查CHO衍生物的Mcmurry偶联和CH2OH衍生物的酸催化偶联以产生相应的（OEP）6衍生物。由前一反应，完全没有得到全亚乙烯基连接的（OEP）6衍生物，仅提供不溶性物质。另一方面，从后者的反应中，乙烯和乙烯基连接的（OEP）6衍生物被成功地分离，其分子结构完全通过MS，PMR和电子吸收光谱的手段确定。结果表明，（OEP）6衍生物基本上具有乙烯基连接的（OEP）3衍生物的电子性质，是乙烯基连接的（OEP）3与乙烯键简单连接的一种二角结构，在本研究中，观察到乙烯基连接的（OEP）3的CHO和CH_2OH衍生物的不对称分子运动，可能是由于这些取代基与周围的乙基取代基之间的空间排斥。也就是说，这些（OEP）3衍生物在室温下具有不对称的分子结构，其中三个OEP环和两个亚乙烯基键分别彼此不同。二乙炔-和乙烯-基团连接（OEP）4衍生物具有对称的分子结构，初步证明它是一种主体分子，能与各种客体分子形成包合物。如果客体分子具有手性，则这种包合络合物应该是手性的。在实际应用中，二乙炔基和乙烯基连接的（OEP）4衍生物与光学活性物质如（R）-或（S）-2-烷醇形成相应的包合物，表现出活跃的圆二色性（CD）光谱行为。因此，目前正在制备大量的乙烯基和亚乙烯基连接的（OEP）6衍生物，以检查其CD光谱行为。少

Oligornerization of the pai-electronic conjugated cyclic system which have wide area and thus highly respond to outside stimulations is a very important methodology for the development of new functional organic materials. Among the pai-electronic conjugated cyclic systems, porphyrin ring system is particularly promising as seen in an example of a special dimer in a photo-synthesis reaction center. Therefore, oligomerization of porphyrin ring with various linkages has been demonstrated to achieve a wide variety of purposive functions such as photocurrent (PC) and electroluminescence (EL). We also previously reported the synthesis of vinylene-group connected octaethylporphyrin trimer, (OEP)3, and studied its electronic property, proving that the electron releasing ability, for instance, outstandingly enhances in order of (OEP) <<(OEP) 2 <<<(OEP)3.Successively to this result, in the present research stint, dimerization of the (OEP)3 component by connecting with ethylene linkage was planne … More d in cider to examine the electronic properties of ethylene- and vinylene-groups connected OEP hexamer, (OEP)6. After several examinations, we were successful in introducing the functional groups such as formyl (CHO) and alcohol (CH2OH) onto the central OEP ring of (OEP)3 selectively. And, both Mcmurry coupling of the CHO derivative and acid-catalyzed coupling of the CH2OH derivative were examined to lead to the corresponding (OEP)6 derivatives. From the former reaction, the all-vinylene-group cannected (OEP)6 derivative was not obtained at all, only affording the insoluble materials. On the other hand, from the latter reaction, the ethylene- and vinylene-groups connected (OEP)6 derivative was successfully isolated, the molecular structure of which was fully determined by means of MS, PMR and electronic absorption spectra. It was proved that the present (OEP)6 derivative substantially possesses the electronic properties of the vinylene-group connected (OEP)3 derivative and thus is regarded as a dime is structure of the vinylene-group connected (OEP)3 simply connected with ethylene linkage.On the way of the present research, an unsymmetrical molecular motion was observed in the CHO and CH2OH derivatives of vinylene-group connected (OEP)3, probably due to the steric repulsion between those substituents and the peripheral ethyl substituents. In other words, these (OEP)3 derivatives were found to possess the unsymmetric molecular structure at room temperature, where both three OEP rings and two vinylene linkages are different from each other, respectively.Furthermore, in relation with these properties of oligomeric (OEP)n derivatives, the diacetylene- and ethylene-group connected (OEP)4 derivative with symmetrical molecular structure has been preliminarily proved to be a host molecule which forms inclusion complexes with various guest molecules. If a guest molecule has a chirality, such an inclusion complex should be chiral. In practice, the diacetylene- and ethylene-group connected (OEP)4 derivative showed an active circuler dichroism (CD) spectral behavior, by forming the corresponding inclusion complexes with optically active substances like (R)- or (S)-2-alkanols. Thus, at present, the preparation of a large quantity of the ethylene-and vinylene-group connected (OEP)6 derivatives is underway to examine its CD spectral behavior. Less