| Metal phosphite and phosphates?MPOs?not only exhibit captivating structures,but also have many applications in the fields of adsorption,separation,gas storage,catalysis,etc.Recent studies have testified that the introduction of polydentate N-containing ligands into MPOs systems could not only enrich the structural composition but also expand the field of properties investigation.According to the hard-soft-acid-base?HSAB?theory,the introduction of rigid linear dipyridineunitsBPB(1,4-bis?pyrid-4-yl?benzene,BPBP?4,4'-di?pyridin-4-yl?-1,1'-biphenyl?and flexible polyimidazole units titmb?1,3,5-tris?imidazol-1-ylmethyl?-2,4,6-trimethylbenzene?into MPOs system gives rise to seven hybrid MPOs,[?Me?2BPBP][Zn?H2PO4?4]?1?,[?Et?2BPBP][Zn?H2PO4?4]?2?,[Zn2?HPO3?2?BPB?]?3?,[H2BPBP]3·[Zn5Cl8?HPO3?4]·H2O?4?,[NH2?CH3?2]2[K@Ni6?HPO3?6?HCOO?3?titmb?2]·3H2O?5?,[Zn3?HPO3?3?titmb?]·2H2O?6?,[Zn3?HPO4?3?titmb?]?7?based on the coordination-directed assembly and template-directed assembly strategies.Single crystal X-ray diffraction?SCXRD?,powder X-ray diffraction?PXRD?,elemental analysis?EA?,infrared?IR?spectroscopy,thermogravimetric analysis?TGA?,photoluminescence?PL?spectroscopy,solid ultraviolet-visible?UV-Vis?spectroscopy,and electron spin resonance?ESR?spectroscopy were used to characterize the structure and corresponding properties of the targeted compounds.The main contains of this thesis are presented as follows:The first chapter mainly introduces the research background of this thesis with focus on the research progress of hybrid MPOs,and clarifies the significance for selecting this area.The second chapter introduces the synthesis and properties of hybrid MPOs based on rigid linear dipyridine derivatives.Four hybrid MPOs based on BPB and BPBP were prepared.Compounds 1 and 2 have the same inorganic unit,in which four partially deprotonated phosphate groups coordinate with Zn2+to form anionic monomer[Zn?H2PO4?4]2-.The BPBP units undergo in-situ alkylation reaction with the corresponding solvent.The alkylated productsserve as counterions to balance the negative charge.Interestingly,each inorganic monomer connects four adjacent monomers through hydrogen-bonds to yield an inorganic anionic supramolecular framework with dia topology.The proton conductivity for compounds 1 and 2 at 100%relative humidity and70°C are 6.11×10-4 S·cm-1 and 6.39×10-5 S·cm-1,respectively.The framework of compound 3 can be deconstructed from the linkage of neutral BPB units and inorganic zincophosphite chains.Under the irradiation of Xe-lamp?300 W?,the colorless single crystal of 3 changes to yellow-brown.The decoloration process could be finished via putting the colored sample in dark for 1 day or heating at 90°C for 30 min.Compound 4features,an anionic pentanuclear zinc cluster with the protonated BPBP units act as charge-balancers.The color of pale-yellow crystalline sample of 4 gets deepened under the irradiation of Xe-lamp.The third chapter introduces the construction and properties of hybrid MPOs based on flexible polyimidazole ligand.In compound 5,the phosphite and in-situ generated HCOO-coordinate with Ni2+ions to form a Ni6 cluster with K+encapsulated in the intracluster cavity.Two titmb moieties are distributed at top and down sides of the cluster via coordination with Ni2+ions.The in-situ generated dimethylamine ion balances the charge of anion cluster.Compounds 6 and 7 possess hybrid layered structure,in which phosphite and partially deprotonated phosphate bridge zinc ions to form a neutral inorganic layer.Organic titmb units are suspended on the two sides of the inorganic layers via bonding with intralayer Zn2+ions.Both of them exhibit room temperature phosphorescence?RTP?behavior.Interestingly,although the structural constituents of 6and 7 are similar,they show distinct RTP behavior,which is mainly attributed to the different configurations of organic titmb units in the resulting hybrid structure.The fourth chapter summarizes the main contents and improvements of this thesis. |
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