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

1.以2-苊[1,2-c]吡咯为原料，制备了卟啉、吡咯-染料等具有高共轭体系的功能化合物。所得卟啉的紫外光谱在sot波段（556 nm）表现出较大的红移，并且在q波段有意想不到的强吸收。采用复古Diels-Alder反应制备了八羧基苯并卟啉。该卟啉的堆积能力随ph值的变化而变化。采用改进的Ugi反应合成了4个含有新氨基酸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）。核磁共振分析清楚地表明，除AA_1， AA_3 = Aib的肽外，含2dpy的三肽均采用独特的构象，在2Dpy-NH与一个吡啶氮之间、AA_3- nh与另一个吡啶氮之间存在两个分子内氢键。这一构象至今未见报道。另一方面，肽Z- aib - 2dpy - aib - ome可能采用β-turn结构，该结构由2Dpy-NH与一个吡啶氮之间以及AA_3-NH与Z基团的C=O之间的两个分子内氢键稳定。合成了新型二茂铁基双视受体。该受体有两个低聚乙二醇臂，在相同的环戊二烯环上有下垂的2,2'-联吡啶单元，Cu(I)阳离子与受体结合，与聚醚组成的腔形成1:1的配合物，所形成的配合物作为氨基酸酯盐的受体，形成双异位配合物。双色络合物的^1H NMR谱在联吡啶区表现出较强的展宽，而同一样品的ESR谱给出了Cu（II）种的信号。根据这些数据，Cu(I)配合物与AAOMe-HCl结合导致构象变化，同时Cu(I)配合物被氧化为Cu（II）配合物。

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.