Design,Synthesis And Properties Of Functional Porous Organic Polymers

The development of porous materials has experienced a series of evolutions from inorganic porous materials(zeolite,activated carbon,diatomite,etc.)to organic porous materials(metal-organic frameworks,porous coordination polymers,porous organic cages,porous organic polymers,etc.).In contrast,porous organic polymer materials possess many advantages,such as high specific surface area,good stability,low density,easy structure regulation and functionalization,and stimulate the strong interest of researchers.The ultimate goal is to realize the practical application of the materials.Therefore,the design and synthesis of porous organic polymers with low cost and practical application properties as well as the expansion of their application will be the new direction of future development.In this paper,based on functional monomer implantation strategy,various functional porous organic polymers have been designed and synthesized from diverse functional building units through different reactions.The structures of the polymers have been characterized by Fourier transform infrared spectroscopy(FT-IR),solid state nuclear magnetic resonance(NMR)spectroscopy,powder X-ray diffraction analysis(PXRD),and X-ray photoelectron spectroscopy(XPS).The morphology and basic properties of the polymers have been investigated by scanning electron microscopy(SEM),transmission electron microscopy(TEM),gas adsorption/desorption and thermogravimetric analysis(TGA).The applications of these polymers in fluorescent sensing,heterogeneous catalysis,and photochemical fields have been studied.The research contents mainly include the following parts:(1)A porous tetraphenylethylene-based polymer for fast-response fluorescence sensing of Fe(?)ion and nitrobenzeneA fluorescent porous tetraphenylethylene-based organic polymer has been prepared by condensation of tetra-(4-(2-aminopyrimidine))styrene with cyanuric chloride,and its permanent porosity has been demonstrated by gas adsorption/desorption experiments.Most importantly,the structure of this polymer contains abundant secondary amine and pyrimidine nitrogen atoms around 1,3,5-triazine units,forming sufficient chelating sites towards metal ions for quickly sensing Fe(III)ion.Also,the response of the tetraphenylethylene-based organic polymer to Fe(III)ion in water is very sensitive and the limit of detection is far lower than the national and international standard water quality index,which establishes a good foundation for the application of this polymer in practical production and life to detect Fe(III)ion.In addition,the fluorescent polymer shows excellent sensitivity and selectivity to nitrobenzene,which is expected to be well applied in explosives detection.(2)Triptycene-based bimetallic salen porous organic polymers for high efficiency CO2 fixation to cyclic carbonatesExposing more active sites of heterogeneous catalysts is very important for catalysis.A series of bimetal salen-based porous organic polymers have been synthesized by 2,3,6,7,14,15-hexaaminotributene,2,6-dimethylform-4-methylphenol and metal salts.Different from the general 2D ?-? stacked porous organic polymer,the triptycene unit was designed to support the arrangement of bimetal salen macrocycles on the side wall of the channel to expose more metal catalytic sites.Bimetallic salen structure has been confirmed by FT-IR,solid state NMR,XPS and inductively coupled plasma optical emission spectrometry(ICP-OES).Gas sorption experimental results have revealed the porosity of the polymers.The isosteric heat of CO2 adsorption of the triptycene macrocyclic polymer containing cobalt is up to 42.1 kJ/mol,indicating the high affinity for CO2.The synergistic effects from their porous nature together with high affinities between CO2 and Lewis acidic metal ions as well as the many active catalytic sites in the channels result in the high efficiency coupling reaction of epoxides with CO2 upon the triptycene macrocyclic polymer containing cobalt metal,realizing the capture and conversion of carbon dioxide.This study not only provides a series of new porous organic polymers,but also builds an effective strategy for heterogeneous catalysis to expose more active sites.(3)Design and synthesis of phthalocyanine-based conjugated planar porous organic polymers for application of singlet oxygen generationA series of crystalline phthalocyanine-based porous organic polymers have been devised and prepared.The structures of the polymers have been characterized by PXRD,FT-IR,solid state NMR and XPS,and the permanent porosity has been verified by gas sorption experiments.In addition,two novel A3B-type asymmetric phthalocyanine crystals have been obtained by using the similar synthesis reaction of the series of phthalocyanine-based polymers in absence of triethylamine,and their structures have been revealed by single crystal X-ray diffraction analysis.The photocatalytic degradation experiments of 1,3-diphenylisobenzofuran illustrate that the series of the polymers could generate singlet oxygen under visible light irradiation,indicating their photosensitizer potential in producing reactive oxygen species.As a result,it is expected to expand the application prospect of phthalocyanine-based porous organic polymers in photochemical fields such as photodynamic therapy.(4)Synthesis,structure,and spectroscopy of novel chiral binaphthalene-linked pyrenesFour novel chiral binaphthylamine linked pyrene compounds have been designed and synthesized,named(R)-/(S)-1 and(R)-/(S)-2,and characterized by a series of spectroscopic methods,including MALDI-TOF mass spectrometry,NMR,electronic absorption spectroscopy and circular dichroism spectroscopy,which demonstrating that the pyrene group has inherent chirality in the whole molecule due to the introduction of chiral binaphthylamine.For the single crystal X-ray diffraction analysis of(R)-1 and(S)-1,the exact structure of diazotized eight-membered ring,producing by the connection of chiral binaphthylamine with pyrene,has been revealed.In addition,the electronic structures of(S)-1 and(S)-2 have been simulated by density functional theory calculations,and the situation of the electron transfer between binaphthylamine group and pyrene chromophores has been clarified.