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

1)我们合成了一系列带有不同长度二氧亚甲基的meso-meso连接的双卟啉。这些双卟啉表现出系统的光谱变化时，在dihendral角的减少。2）制备并表征了meso-meso连接卟啉阵列的1024-mer离散分子，这是迄今为止最长的人造离散分子。3）Sc（OTf）_3和DDQ氧化实现了端苯基封端的meso-meso连接卟啉阵列向三氟甲基连接的共轭卟啉阵列的高效转化。这些共轭的6-mer、8-mer和12-mer的吸收光谱显示电子吸收带深入到红外区直到1500 cm ~ 2<-1>。从5，10-二芳基金属卟啉出发，以10-15%的产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.