Construction of Molecular Chain Reaction Synstem Based on Porphyrin Arreys and Chain Protochemical Reactions

1)制备了一系列以变长二氧亚甲基为链结的中-中链偶卟啉。这些双卟啉在二面角减小时表现出系统的光谱变化。非束缚双卟啉的双带形态变为四带形态。2)制备并表征了离散的1024- meo -meso - linked卟啉阵列，这是迄今为止最长的人造离散分子。值得注意的是，即使是1-240mer也肯定可溶于有机溶剂，并且可以进行操纵。3) Sc(OTf)_3和DDQ氧化实现了末端苯基包封的中介孔连接卟啉阵列向三连接共轭卟啉阵列的高效转化。共轭6-mer、8-mer和12-mer的吸收光谱显示出深红外区域的电子吸收带，最高可达1500 cm^<-1>。以5,10-二芳基金属卟啉为原料，以10-15%的收率制备了具有二维扩展π网络的共轭矩形卟啉片。

1) We have prepared a series of meso-meso linked diporphyrins strapped with variable length dioxymethylene group. These diporphyrins exhibit systematic spectral changes upon the decrease in the dihendral angle. Two-bands shape Soret band in non-strapped diporphyrins changes into four-bands shape Soret band.2) Discrete 1024-mer of meso-meso linked porphyrin arrays has been prepared and charactrized, which is by far the longest man-made dicrete molecule. It is to be noted that even 1-240mer is certainly soluble in organic solvents and can be manipulated.3) Oxidation with Sc(OTf)_3 and DDQ realized very efficient transformation of end-phenyl capped meso-meso linked porphyrin arrays to triply-linked conjugated porphyrin arrays. The absorption spectra of these conjugated 6-mer, 8-mer and 12-mer display the electronic absorption band deep into infrared region up to 1500 cm^<-1>.Starting from 5,10-diaryl metalloporphyrin, conjugated rectangular-shaped porphyrin sheets have been prepared in 10-15% yields, which have 2-dimensionally expanded π-network.