Luminescence and Adsorption Properties of Metal Organic Complex and Derivatives

Author:Wang A Ni

Supervisor:hao su e fan rui qing


Degree Year:2019





Quinolinaldehyde and aniline,p-methylaniline,o-methylaniline,2,6-dimethylaniline,2,6-diethylaniline,2,6-diisopropylaniline,p-nitroaniline and the metal salts of Zn(II),Cd(II)and Hg(II)were reacted to synthesize 11 kinds of imine metal organic complexes 1–11.The phenanthroline aldehyde and o-phenylenediamine,4-methyl-o-phenylenediamine and Zn(II)metal salts were selected to synthesize 4 kinds of benzimidazole metal-organic complexes 12–15.Derived materials were prepared based on 12–15.The structures of 1–15 were characterized by single crystal X-ray diffraction,elemental analysis,infrared spectroscopy,nuclear magnetic resonance spectroscopy,scanning electron microscopy,etc.,and the luminescence and adsorption properties of 1–15 and its derivatives were studied.Finally,theoretical calulations were used to verify the experimental results,revealing the relationship between structure and performance.Ligand(E)-4-methyl-N-((quinoline-2-yl)ethylidene)aniline(L)was been synthesized by reactions of 2-quinolinecarboxaldehyde and p-methylaniline.Five metal organic complexes 1–5 were synthesized.The crystal structures of these complexes indicate that noncovalent bond interactions,such as hydrogen bonding C–H···Cl/O andπ···πstacking,play essential roles in constructing the supramolecular structures(1D,2D,3D).The luminescence properties of complexes 1–5 are investigated,strong greenish luminescencent emission was found in the aggregate state.Moreover,enhanced emission intensity was induced by mechanical grind and temperature also attributed to the AIE properties.Subsequently six different substituted of Zn(II)AIE organic molecules,6–11,were synthesized based on the corresponding six ligands L1–L6 to detect water in different organic solvents,including dimethyl sulfoxide,dichloromethane and methanol with broad detection ranges.Interestingly,the molecule of Zn(II)complexes demonstrated an aggregation-induced emission response to water.In spite of the fluorescence enhancement of Zn(II)complexes owing to the AIE phenomenon,the mechanism is speculated to the novel water-activated hydrogen-bonding crosslinking AIE(WHCAIE).The WHCAIE can work regardless of how much water subsistence in the system,getting a broad detection region(0.2%–94%).In order to extend conjugate system,metal-organic complexes 12 and 13 have been hydrothermally synthesized by using 2-carboxaldehyde-1,10-phenanthroline,o-phenylenediamine and ZnCl2.In addition,metal-organic complexes 12 and 13 air filters are produced under 80°C for only 5 minutes by using hot-pressing method,including carbon fiber cloth,plastic mesh,glass cloth,melamine foam.Under the applied pressure and temperature,2-carboxaldehyde-1,10-phenanthroline,o-phenylenediamine,ZnCl2,12 and 13 crystals can well fasten on the surface of flexible substrates.We also obtained layer-by-layer 12 and 13 coatings,producing five cycles of 12 and 13 coatings on the various substrates.Owing to the larger conjugation system,micropore structure,lower pressure drop and electron cloud exposed metal center of 13(DFT calculations),13@melamine foam–4 gives the highest removal rates.PM2.5:99.5%±1.2%and PM10:99.3%±1.1%,and the removal efficiency for capture PM2.5 and PM10 particles in cigarette smoke were both retained at high levels(>95.5%)after a 24 h test.Moreover,PMs removal efficiency of13@melamine foam–4 based breathing mask shows higher removal efficiency,lower pressure drop,smaller thickness and higher quality factor than two commercial breathing masks.For further obtain the composite material with high surface areas and pore volumes,we investigate for the first time that two different N-content pyridine-ligand metal–organic complexes(14 and 15)as precursors to prepare the N-doped porous carbons(noted as NPC-1-T and NPC-2-T,T represents the carbonization temperature)through the carbonization process in this work.At different carbonization temperatures(800,900,1000 and 1100°C),the surface areas and pore volumes reach as high as 1656.2 m2 g-1 and 1.29 cm3 g-1,the N content reaches up to 16.61%for resulting N-doped porous carbons,especially,the content of pyridinic-N up to 7.3%,therefore,the NPC-1-900 shows a significant amount of SO2 adsorption,over 118.1mg g-1 at 1 bar and 25°C.Theoretical calculation indicated that pyridinic-N doping into carbon lattice could affect on electrostatic surface potential and the local electronic density,for enhancing SO2 adsorption.