Constructing Functional Organic Conjugated Materials Via Macromolecular And Supramolecular Chemistry Strategies

Organic conjugated functional materials play an important role in many fields. As a branch of polymer chemistry, the porous organic polymers attract much interests from both chemists and material scientists. Because these polymers possess porosity, high thermal stability and chemical stability, synthesis diversification, easy functionalization, etc. So the polymers were applied in various fields, for example:gas adsorption and storage, aggregation induce emission, energy storage and conversion, chem-& bio-sensing, heterogeneous catalysis and electrical properties. We designed and synthesized two kinds of porous organic polymers which contained different conjugated structures, its adsorption and fluorescence properties were explored. On the other hand, due to the potential application of salphen-based supermolecules on solar adsorption and conversion, heterogeneous catalysis, membrane separation etc, a kind of salphen-based molecules were designed and synthesized, and their self-assembly behaviors were preliminarily investigated. We hope our work could be useful for others in the near future.Our work manly consists of three parts:(1) four conjugated microporous polymers and their repeating units were synthesized via Knoevenagel reaction of 1,3,5-Benzenetricarboxaldehyde, tri(4-formylphenyl)amine, 4')4''',4""',4"""-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'-biphenyl]-4-carbaldehyde)), tetrakis(4-formylphenyl)methane and 1,4-phenylenediacetonitrile or phenylacetonitrile. First, the polymers and their repeating units were mearsured by infrared spectroscopy. The conjugation degree of CMPs is larger than their units from their fluorescence photos under ultraviolet irradiation. These polymers were fully characterized by fluorospectrophotometer, BET surface area analyzer, SEM, TEM, TGA, XRD, UV-vis, Steady-Transient Fluorescence Spectrometer, elemental analysis. We observed that the CMPs own large specific surface areas. The specific surface areas of four CMPs, namely Bn-CS-CMP, TPA-CS-CMP, TPE-CS-CMP, TPM-CS-CMP are 339 m2g-1,615 m2g-1?-459 m2 g-1?903 m2 g-1, respectively.(2) five conjugated microporous polymers were synthesized by glaser coupling reaction from 1,3,5-tris-(4-ethynylphenyl)benzene, tri(4-ethynylphenyl)amine, tetrakis(4-ethynylphenyl)methane,2,2',7,7'-tetraethynyl-9,9'-spirobi[fluorene], 1,1,2,2-tetrakis(4-ethynylphenyl)ethane. All the five polymers could form gel after reaction. These polymers were characterized by, for example, IR, BET surface area analyzer, TEM, TGA, XRD and solid-state NMR. Their morphologies were very uniform and possessed large specific surface areas, high thermal stability. The largest CO2 uptake capacity was 12.88mg g-1.(3) 4,5-bis(dodecyloxy)-2-hydroxybenzaldehyde reacted with 1,2,4,5-tetraamino-benzene tetrahydrochloride or HATP*6HC1, producing the molecule 1 (M1) and molecule 2 (M 2), respectively. The two molecules coordinated with Zn2+, Cu2+ to form four supermolecules, namely PSZn, PSCu, TSZn3, TSCu3, respectively. PSZn, TSZn3, TSCu3 could form stable physical gels in many solvents.