Synthesis,Crystal Structure And Optical Properties Of Hexaazamacrocyclic Metal Complexes

Macrocyclic coordination chemistry is a subject based on the synthesis, structure, properties and applications of cyclic complexes from multidentate ligands whose frameworks contain O, N, S, P, Se, As, et al donor atoms. Among these fields, azamacrocyclic metal complexes used as building blocks to construct macrocyclic metal bridging complexes with bridging ligands have attracted more and more attention in the fields of crystal engineering, coordination chemistry and material chemistry, not only because of their intriguing network topologies, but also because of their potential applications in molecular recognition, magnetism, molecular catalysts, ion-exchange, non-linear optics, solid luminescence and gas absorption etc.This dissertation employed hexaazamacrocyclic metal complexes as building blocks reacting with different bridging ligands, eight new azamacrocyclic metal complexes were designed, synthesized and characterized by X-ray single-crystal crystallographic analysis, elementary analysis (EA), infrared spectra (IR), X-ray powder diffraction (XRD), solid-state fluorescent spectra and UV-vis spectra. We investigated their luminescent properties and electronic absorption spectral characteristics. This thesis contents and main results are as follows:1. Three hexaazamacrocyclic metal precursor complexes [Ni(A)]Cl2·2H2O (1) (A=1,3,6,9,11,14-hexaazacyclooctadecane), [Ni(B)](ClO4)2 (2) (B=1,3,6,8,11,14-hexaazacyclooctadecane), [Cu(C)](ClO4)2 (3) (C=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane) were synthesized by template methods with ethylenediamine, diethylenetriamine, triethylenetetramine or ethanolamine as starting materials. These complexes have been characterized by EA, IR, XRD showed that the synthesized of complexes as pure compounds, can be used as building blocks.2. Complexes 1-3 were employed as building blocks reacting with different bridging ligands, designed and synthesized eight novel hexaazamacrocyclic metal complexes: trans-[Ni(C12H26N6)(N3)2] (4),{[Ni(C12H26N6)][Ni(CN)4]}n (5),{[Ni(C12H26N6)(bdc)]·8H2O}n (6), {[Ni(C12H26N6)(Hbtc)]·3H2O}n (7),{[Ni(C12H26N6)(H2btec)]}n (8),{[Ni(C12H26N6)(bdc)]·3H2O}n (9),{[Ni(C12H26N6)(bdc)]·2H2O}n (10) and [Cu(C12H30N6O2)(H2btc)2] (11). Crystal structure analysis showed that in the synthesized of these complexes metal ions have similar coordination environment and coordination geometry. The metal ions have an axially elongated distorted octahedral geometry with four nitrogen atoms from the hexaazamacrocycle ligands and two coordination atoms from two bridging ligands.3. Two-dimensional brick wall structure by N-H...N hydrogen bonding interaction in complex 4, eight water molecules family structure in compound 6, two-dimensional lattice structure by weak coordination bonds interaction in complex 8, and H3btc with Hbtc2- and anions forms existed in compounds 7 and 11. These coordination structures are relatively peculiar structural features. Have similar structural features of complexes are rarely reported.4. IR, XRD and UV-vis absorption spectra analysis results of complexes 4-11 further proved that the measured crystal structure are these complexes structure.5. Fluorescent properties studies revealed that complexes 1-11 displayed a good luminescent properties in the solid state at room temperature, can be used as luminescent materials application in the fields of optical materials.In summary, this dissertation designed and synthesized eight novel hexaazamacrocyclic metal complexes, which enriched the types of azamacrocyclic metal complexes. Some complexes have good optical properties, provided a good experimental material for design, synthesis and function of development of functional complexes.