Synthesis And Properties Research Of Cvclen-based Derivatives And Their Complexes

Macrocyclic polyamine ligand1,4,7,10-tetraazacyclododecan(cyclen) and its derivatives have good chelating abilities. They can formstable complexes with many metal ions and these complexes are widelyused in the fields of catalyst, molecular recognition, fluorescent probe,artificial nuclease and self-assembling. So it has important significance todesign and synthesize cyclen derivatives and their metal complexes. Inthe thesis cyclen was used as a matrix and modified with differentnitrogen-containing group to be cyclen derivatives ligands. Then weintroduced different metal ions to create a batch of metal complexes. Andwe also studied some properties of these complexes.This thesis is composed of three chapters. Chapter1introducesbriefly the background knowledge relevant to cyclen derivatives and theircomplexes. The properties and applications of these complexes areintroduced, too.In chapter2, we modified cyclen with terpyridine group to get twoligands: mono-substitution cyclen derivative,1-[4’-p-tolyl-(2,2’:6’,2’’-terpyridyl)]-1,4,7,10-tetraazacyclododecane (L1), and bi-substitutioncyclen derivative,1,7-bi[4’-p-tolyl-(2,2’:6’,2’’-terpyridyl)]-1,4,7,10-tetraazacyclododecane (L2). Five mononuclear metal complexes and twodinuclear metal complexes were prepared by introducing different metalactive centers. Ligands and complexes were characterized by H-NMRspectrum, infrared spectroscopy and electrospray ionization massspectrometry. And the Optical properties and electrochemical propertiesof these complexes were studied. In chapter3, we modified cyclen with pyridine by connecting withamide bond to get mono-substitution cyclen derivative1-[N-(2’-(2’’-pyridy)ethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane (L3) and1-[N-(2’-(3’’-pyridy)ethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane (L4). Three different heterodinuclear complexeswere synthesized by introducing different metal active centers. Ligandsand complexes were characterized by H-NMR, IR and ESI-MS. We alsostudied optical properties, electrochemical properties and cytotoxicactivity in vitro of these heterodinuclear complexes. Because of theintroduction of platinum center, these complexes have certain antitumoractivity. These findings provide some ideas for the design of anticancerdrug in the future.