Synthesis of functional molecules using the stacking interaction and hydrogen bonding of porphyrins, and their chemical and physical properties.

1.以2-苊并[1，2-c]吡咯为原料，合成了卟啉、吡咯亚甲基染料等具有高度共轭体系的功能化合物。所得卟啉的紫外光谱除了Q带的强吸收外，还表现出与Soret带（556 nm）的大的红移。利用逆Diels-Alder反应合成了八羧基苯并卟啉。2.用改进的Ugi反应合成了4个含新型氨基酸α，α-二（2-吡啶基）甘氨酸（2Dpy）的三肽（Z-AA_1-2Dpy-AA_3-OMe ; AA_1，AA_3 = Gly，Aib）。NMR分析表明，除AA_1，AA_3 = Aib外，含2Dpy的三肽均为独特的构象，分子内有两个氢键，分别位于2Dpy-NH和AA_3-NH之间。这种构象至今未见报道。另一方面，Z-Aib-2Dpy-Aib-OMe可能具有β-转角结构，2Dpy-NH与吡啶氮之间以及AA_3-NH与Z基团的C=O之间存在两个分子内氢键。该受体具有两个寡聚乙二醇臂，在相同的两个环上具有侧接的2，2 '-联吡啶单元，Cu（I）阳离子与受体结合，与由聚醚组成的空腔形成1：1的络合物，所形成的络合物作为氨基酸酯盐的受体，得到双配位络合物。双配位配合物的^1H NMR谱在联吡啶区域表现出强烈的增宽，同一样品的ESR谱给出了被指定为Cu（II）物种的信号。根据这些数据，Cu（I）络合物与AAOMe-HCl的结合导致构象变化，同时Cu（I）络合物被氧化为Cu（II）络合物。

1.Porphyrin, pyrromethene-dye, and other functional compounds with highly-conjugated systems were prepared from 2-acenaphtho[1,2-c]pyrrole which showed strong stacking ability. The UV spectrum of the resulting porphyrin exhibits large red shifts with the Soret-band (556 nm), besides the unexpected strong absorption of Q-band. Octa-carboxylbenzoporphyrin was also prepare using retro Diels-Alder reaction. The stacking ability of this porphyrin varies depending on the pH.2.Four tripeptides (Z-AA_1-2Dpy-AA_3-OMe ; AA_1, AA_3 = Gly, Aib) containing a novel amino acid, α,α-di(2-pyridyl)glycine (2Dpy), were synthesized by the modified Ugi reaction. NMR analysis clearly indicated that the 2Dpy-containing tripeptides except the peptide in which AA_1, AA_3 = Aib, adopt a unique conformation with two intramolecular hydrogen bonds between 2Dpy-NH and a pyridine nitrogen and between AA_3-NH and another pyridine nitrogen. This conformation has so far not been reported. On the other hand, the peptide Z-Aib-2Dpy-Aib-OMe probably adopts a β-turn structure which is stabilized by two intramolecular hydrogen bonds between 2Dpy-NH and a pyridine nitrogen and between AA_3-NH and the C=O of the Z group.3.The novel ferrocene-based ditopic receptor was synthesized. This receptor bears two oligoethylene glycol arms with pendant 2,2'-bipyridine unit at the identical cyclopentadienyl rings, Cu(I) cation binds to the receptor to form 1:1 complex with the cavity consisting of polyether, and the resulting complex acts as a receptor for amino acid ester salts to give the ditopic complex. The ^1H NMR spectrum of the ditopic complex exhibits strong broadening at the bipyridine region, and the ESR spectrum of the same sample gives the signals assigned as Cu(II) species. With these data, the binding of Cu(I) complex towards AAOMe-HCl leads to the conformational change, and the Cu(I) complex is simultaneously oxidized to Cu(II) complex.