The Coordination Polymers With Active Sites Of Synthesis, Structure And Properties

The chemical sensing and detection play a crucial role in environmental monitoring, medical science, and industrial production. Wherein, the metal-organic frameworks (MOFs) are of great interest as sensing materials, owing to that they possess prominent optical properties, tunable structures, and relatively long emission wavelengths have emerged as required and usher in a rapid development. Especially, those with functional sites, such as open metal sites, catalytically metal sites and active functional group srapidly stand out for the quick response, convenient applications, low cost and so on. To date, scientists have developed all kinds of MOFs sensors in various application fields.Considering all the aspects stated above, we choose a V-shaped multiple carboxylic ligand and a linear nitrogen-containing ligand with the active site and choose inhomogeneous second ligands with the active sites. We have synthesized eleven coordination polymers. We study that the luminescent sensing mechanisms towards Fe3+ of compounds 1-3. Me2NH2@MOF-10 can highly selective and sensitive electrochemical sensor of Cu2+ ion. Me2NH2@MOF-10 and Me2NH2@MOF-11 may highly selective sensing luminescence of Tb3+ ion.There are five chapters in the paper:Chapter 1, we give the development and concept of metal-organic complexes, structures and influencing factors. Finally, we introduce the applications and progress of metal-organic complexes.Chapter 2, the two novel porous luminescent MOFs have been constructed and systematic quenching mechanisms have been explored from the view point of dynamic and static behaviors by using concentration-dependent lifetime measurements and time-dependent intensity experiments. Dynamic and static quenching behaviors of MOFs sensors have been seldom explored, while this work not only conducted systematic exploration on dynamic and static behaviors, but also proposes a facile suggestion on the future design of highly functional LMOF sensors.Chapter 3, we have successfully synthesized and characterized a series of compounds, namely, [Zn(bpyp)(L-OH)]n·DMF·2H2O (3), [Zn(bpyp)1/2(L-NH2)]n·2H2O (4), [Zn(bpyp)(dL)]n·3H2O (5), [Zn(bpyp)(HL)]·H2O (6), [Zn(bpyp)(L-NO2)] (7), [Zn3(bpyp)(tcb)2]·DMF (8), and [Zn(bpyp)(Hbba)]·2DMF·H2O (9), based on 2,5-bis(pyrid-4-yl)pyridine ligand by hydrothermal synthesis method. Compound 3, which may more easily create static quenching that compounds 1 and 2. Besides, the corresponding dynamic and static quenching constants are calculated, achieving the quantification evaluation of the quenching process. This work not only achieves the quantitative evaluation of the luminescence quenching but also provides certain insights into the quenching process, and the possible mechanisms explored in this work may inspire future research and design of target LCPs with specific functions.Chapter 4, we first developed the new composite of microporous anionic Me2NH2@MOF-10 using it modified electrode with Au nano-particle on glassy carbon electrodes. The modified electrode showed an excellent selectivity, high stability, high sensitivity, wide linear range and lower detection limit for copper (?) because of the 3D porous nano-structured together with the synergism of gold nano-particles and the cationic change of Me2NH2@MOF-10, which would accelerated ions transfer, provided an active surface area of electrode and an unimpeachable cationic change passageway between electrode and copper (?) ions. The result of speciation and recovery about copper (?)in river water spiked with known concentration demonstrated that the Au/Me2NH2@MOF-10/GCE electrode has promise for determination of copper (?) in real samples such as river water samples. We believe this work for generating new electrode materials will be useful for preparing new sensors and reporters for electrochemical systems.Chapter 5, Me2NH2@MOF-10 can incorporate lanthanide cations via a simple cation exchange process and selective sensitize Tb3+cation. The cationic change can be assigned to the pore and cationic size is match and the ionic interaction with the anionic framework Me2NH2@MOF-11 can via a cation exchange process and selective sensitize Eu3+ and Tb3+ cations. This selective sensitization of cations is realized due to the facile energy transfer to the excited state of Eu3+ and Tb3+ from the singlet excited states of framework. Further, we showed that the Tb3+ uptake and release is a reversible process. These results demonstrate that Me2NH2@MOF-11 can reversible and selectively serve as an antenna for sensitizing the visible-emitting Tb3+ cation. This strategy for generating new luminescent lanthanide materials will be useful for preparing new sensors and reporters for biological systems.