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

1.以具有较强堆积能力的2-萘并[1，2-c]吡咯为原料，合成了具有高度共轭体系的卟啉、吡咯染料等功能化合物。所合成的卟啉的紫外光谱除了在Q带有意想不到的强吸收外，还与Soret带(556 Nm)有很大的红移。还采用逆Diels-Alder反应合成了8-羧基苯并卟啉。通过改进的乌吉反应合成了含有新氨基酸α，α-二(2-吡啶)甘氨酸(2Dpy)的四个三肽(Z-AA_1-2Dpy-AA_3-OMe；AA_1，AA_3=Gly，Aib)。核磁共振分析清楚地表明，除AA_1，AA_3=AIB外，2Dpy-NH与一个吡啶氮之间和AA_3-NH与另一个吡啶氮之间存在两个分子内氢键，具有独特的构象。到目前为止，这种构象还没有报道。另一方面，Z-AiB-2Dpy-AiB-OMe可能采用β-Turn结构，这种结构是由2Dpy-NH与吡啶氮之间以及AA_3-NH与Z基团的C=O之间的两个分子内氢键稳定的。该受体在相同的环戊二烯基环上带有两个带有2，2‘-联吡啶单元的低聚乙二醇臂，铜(I)阳离子与该受体结合形成1：1的聚醚空腔，生成的络合物作为氨基酸酯盐的受体而得到异位络合物。重位络合物的~1H核磁共振谱在联吡啶区表现出较强的展宽，同一样品的ESR谱给出了归属为铜(II)物种的信号。根据这些数据，铜(I)络合物与AAOMe-HCl的结合导致构象变化，同时铜(I)络合物被氧化成铜(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.