Structures, Properties And Role Of Anion Effect Of Azolylterpyridine Complexes With Two-photon Absorption

Optical functional materials play an important role in modern information technology industry. People pay more attention to the optical functional complexes because of their excellent thermal stability and optical activity. Design functional organic molecules to obtain functional complexes with preeminent optical properties are significant in the future development of coordination chemistry. Terpyridine is a very important tridentates chelating ligand, which can use to design and synthesize functional terpyridine derivatives with a good chelating ability to transition metal ions, meeting the basic requirements for the realizing organic/inorganic hybrid and optimizing the optical properties. In this work, we synthesized three D-π-A type2,2':6',2"-terpyridine-based ligands (L1, L2and L3), introducing azoles group into the terpyridine through solid state reactions. Self-assembly of the ligands (L1and L2) with d10metal salts yielded a scries of new coordination complexes with special structures and properties. Details are as follows:1. The recent developments in the research for two-photon fluorescence complexes were reviewed and the idea of designing of this dissertation was put forward based on related literatures.2. Three novel2,2':6',2"-terpyridine-based ligands (L1,L2and L3) were synthesized by means of Aldol, Michael addition, Wittig reactions. All the ligands were characterized by IR,1H NMR, MS spectra and Elemental analysis. Single-and two-photon optical properties of the ligands were investigated. Two-photon optical storage was also carried out.3. Self-assembly of the ligands (L1and L2) with d10metal salts MX2(M=Zn, Cd, Hg, X=C1, Br,1, SCN, CIO4) yielded a series of new coordination complexes with special structures and properties. Complexes used for single crystal resolved were determined by single crystal X-ray diffraction analysis. We analysed the coordination model, discussed the type and the size of weak interactions in the super molecules and studied various weak interactions effect on the final topological structures.4. Single-and two-photon optical properties of the complexes were detailedly described. Experimental results revealed that two-photon absorption cross-section of these complexes are extraordinary larger than that of ligand. Besides, with the same metal cation, the two-photon absorbance cross-section vary by the order of Br>SCN>I. The crystal structures of complexes containing MCI2have not been obtained. From elemental analysis data, it is difficult to determine the coordination mode and take the modulus calculation. Thus, density functional theory (DFT) calculation was performed the halogen (Br and I) and pseudo-halogen (SCN) to calculate the accepting capability of these complexes. The results indicate the TPA cross-section vary by the order of Br>SCN>I, which is consistent with the experiment.