Synthesis And Property Investigations Of Superamolecules Based On Spirobifluorene And Adamantane Framework

Supramolecular chemistry is a science that study the molecules aggregates formed by intermolecular noncovalent interactions.It is mainly concerned with the weak interactions of noncovalent bonds.Meanwhile,hydrogen bonding and ?-?interactions are the two most common noncovalent interactions.As an emerging class of highly ordered crystalline porous materials with high surface area,tunable pores,diverse structure and low density,hydrogen-bonded organic frameworks(HOFs)bear excellent application prospects in the fields of gas storage and separation,chemical sensing and proton conduction,and have become one of the new research hotspots in chemistry and material science.Therefore,design and synthesis of functional HOFs materials is an important topicIn this thesis,11 novel supramolecular structures were prepared by using the synthesized spirobifluorene and adamantane derivatives,and their structure and properties were investigated by X-ray single crystal diffraction,powder X-ray diffraction(PXRD),infrared spectroscopy(IR),thermogravimetric analysis(GA)and fluorescence spectra.The main contents are as follows(1)Supramolecule 1 was obtained by the solvent diffusion method based on the synthesized 2,2',7,7'-tetracyano-9,9'-spirobifluorene(TCSBF).Supramolecule 2 was further constructed by 2,2',7,7'-tetrakis(2,4-diamino-1,3,5-triazin-6-yl)-9,9'-spirobifluorene(TDASBF),which was synthesized by TCSBF.The investigations show that supramolecules 1 and 2 have good thermal stability,solvent stability and fluorescence properties.Nitroaromatic compounds have a certain degree of fluorescence quenching effect on them.Meanwhile,supramolecule 2 bears selective fluorescence quenching effect on 2,4-dinitrophenylhydrazine(2)Supramolecules 3 and 4 were obtained by assembly of 2,2',7,7'-tetrakis(4-cyanophenyl)-9,9'-spirobifluorene(TCPSBF),which was synthesized by lengthing with a benzene ring on basis of TCPSBF.And the conversion of single crystal to single crystal can happen between them.2,2',7,7'-Tetrakis(4-(2,4-diamino-1,3,5-triazin-6-yl)phenyl)-9,9'-spirobifluorene(TDAPSBF)was further prepared by TCPSBF,and supramolecules 5-7 were constructed by adjusting solvents and temperature based on TDAPSBF.The investigations show supramolecules 3-7 bear good thermal and chemical stabilities,and nitrobenzene compounds have fluorescence quenching performance for supramolecules 3 and 7(3)Two adamantane derivatives,1,3,5,7-tetrakis(4-cyanophenyl)adamantine(TCPA)and 1,3,5,7-tetrakis(4-(2,4-diamino-1,3,5-triazin-6-yl)phenyl)adamantine(TDAPA),were designed and synthesized.Trough the solvent diffusion method,supramolecules 8 and 9 were obtained by the assemably of TCPA,and supramolecules 10 and 11 were constructed by the self-assembly of TDAPA and 1,5-naphthalenedisulfonic acid(1,5-NDSA).The investigations show that supramolecules 8 and 9 all have stable structures by the C-H…N and C-H…?interactions,and 9 can convert to 8 by heating or immersing into organic solvents.8 and 9 bear fluorescence quenching performance for the nitroarmatic compounds to some extent,but 1,3-dinitrobenzene has special fluorescence enhancement property for 8.Supramolecules 10 and 11 are three dimensional structures by the N-H…O and C-H…O hydrogen bonds.Meanwhile,supramolecules 10 has one dimensional pores.