4 '- Pyridine Replace - Sanlian Pyridine Synthesis, Structure And Properties Of Coordination Polymer Research

The design and synthesis of novel functional coordination polymers which have interesting and useful structure have become a hot topic in coordination chemistry and crystal engineering. Eighteen coordination polymers have been designed and synthetized successfully with4’-pyridyl-terpyridine ligands. The X-ray single crystal diffraction, IR spectra, luminescence spectra and thermal gravimetric analysis have been carried out to characterize the coordination polymers. In this dissertation, it includes the following five parts:(1) Chapter1:Introduction, the basic theory and concept of coordination chemistry, supramolecular chemistry, crystal engineering, coordination polymer and molecular photochemistry have been introduced briefly. In addition, the advance of the4’-substituted terpyridine coordination polymers have also been briefly introduced.(2) Chapter2:Four isomeric4’-pyridyl-terpyridine ligands have been designed and synthesized. Eight ZnⅡ/CdⅡ coordination polymers (1-8) with4’-(2-pyridyl)-4,2’:6’,4’ terpyridine and different organic acids have been synthsized. Compounds1and8show same double-helix structures, compounds2-5show2D grid structures and compounds6and7show a spurious2D two-fold interpenetrations structure. The effection of pH values and anions of metal salts to the structures have also been discussed. The luminescence properties of1-8have been investigated by emission spectra. Additionally, these eight compounds possess great thermal stability, all of them can be stable up to around350℃.(3) Chapter3:Six novel ZnⅡ/CdⅡ coordination polymers (9-14) with4’-(3-pyridyl)-4,2’:6’,4"-terpyridine and different organic acid have been synthesized. The structures are from1D chain (9),2D layer (12).3D structure (13) to3D two-fold interpenetration structure (10,14) and3D three-fold interpenetration structure (11). Compounds9-14show strong luminescence and high stability.(4) Chapter4:Four ZnⅡ coordination polymers (15-18) were synthesized by the reaction of zinc(II) salts with4’-(2-pyridyl)-3,2’:6’,3"-terpyridine or4’-(3-pyridyl)-3,2’:6’,3’ terpyridine with different organic acids. In compounds15and17, two kind of acids were used, but a similar grid layer structure was obtained. Compounds16and18show a3D two-fold interpenetration structure. Compounds15-18still have strong luminescence and high thermal stabilities.(5) Chapter5:As combined the terpyridine coordination polymers we synthesized before, we found that all outer pyridyl groups are twisted with respect to the central one. Besides, the synthesed success rate of the3,2’:6’,3"-terpyridine coordination polymers are lower than others. The reason is that for the2’ position of the base terpyridine,3-pyridyl is not good for stretch as4-pyridyl and it’s also not good for chelate as2-pyridyl.