Synthesis And Performance Study Of Novel Conjugated Macrocycles With Aromatic Heterocycles

Conjugated Arylene-Ethynylene-Macrocycles(AEMs) compounds with their unique structure can maintain certain shapes in solution or in the solid phase, which have special supramolecular properties, such as self-assembly, molecular recognition and host-guest chemistry, as well as unique photoelectric performances. On the other hand, the development of organic optoelectronic materials of small-conjugated molecular’s research is very fast. However, there is little research about AEMs with hetero-aromatic units on their skeleton and its potential properties in nanoscale supramolecule & organic optoelectronic materials field until now.The main content of this thesis including the systhesis of three rigid conjugated macrocycles(4B2A, 3B2 A and 3B3A), which have special aromatic heterocycles on their macrocycles’ skeletons. From the point of molecular structural, these three cyclic compounds have similar structural, all with alternant electro-rich triphenyl-amine unit(A) and electron-poor benzothiadiazole unit with two thiophenes moiety(B), connect with ethynyl or butadiynyl bonds to form D-π-A structure. The related intermediates and target macrocyclic molecules’ structures were determined & confirmed by methods of1 H NMR,13 C NMR, GC-MS and MALDI-TOF MS. In addition, the thermogravimetric analysis(TGA) showed that the corresponding temperature for 5%weight-loss of the 4B2 A macrocycle molecule is 335 ℃, indicating the good thermal stability of the rigid & conjugated 4B2 A ring.These macrocycles’ supramolecular performance in solution with metal ions, and with fullerences of C60 and C70 were tested by ultraviolet absorption and fluorescence emission spectrum, the mainly research results show that:The fluorescence emission spectras showed that the fullerence(C60 & C70) could associate with the macrocycle compound(including all the three macrocylces) andreduce its fluorescence intensities, the more ratio of the fullerences in the solution, the lower fluorescence intensities could be observed, which means that the electronic rich system of the macrocyclic molecules could combine the extremely electronic-poor unit of the fullerene molecules and formed an electronic transfer complex in the toluene solution. Its association constant is K4B2A-C60= 13259, K4B2A-C70= 28700,K3B2A-C60= 19482 and K3B2A-C70= 42980 and K3B3A-C60 = 10880, respectively. The larger association constant of macrocyle-C70 than that of macrocyle-C60, maybe because of the more electric-poor properties of C70 than C60.Their association ratio information were tested by the Job’s titration, the results showed that one 4B2 A and 3B2 A molecule can associate two moleculers of fullerence to form 4B2A:2C60 and 4B2A:2C70, 3B2A:2C60 and 3B2A:2C70 complex,respectively. Which is very rare reported that one conjugated macrocycle can combine two fullerene molecules.By comparing the UV absorbance and fluorescence emission spectra of the three kinds of macrocycles--4B2 A, 3B2 A and 3B3 A in the toluene solutions, we found that these macrocycles have almost same spectrum, the reason is that these three compounds have very similar molecular structures and size.