Development of Red-Emissive Mechanoresponsive Polymers Incorporating Dynamic Photoluminescent Copper(I)-Pyridinophane-Arylamide Mechanophores

Abstract

Okinawa Institute of Science and Technology Graduate UniversityDoctor of PhilosophyThis thesis describes the preparation, photophysical studies and computational studies of the photoluminescent copper(I)-pyridinophane-arylamide complexes, as well as the mechanoresponsive properties of poly(butyl acrylate) films incorporating these complexes as cross-linkers. First, an introduction will be given on the recent development of mechanoresponsive polymers covalently incorporating organic or organometallic mechanophores. The metal complex-based mechanophore systems will be then introduced, followed by the previous work in our group on the development of copper(I)-iodide and copper(I)-NHC photoluminescent mechanophores bearing a conformationally dynamic N4 pyridinophane macrocyclic ligand. In the following chapter, novel copper(I)-pyridinophane-arylamide complexes will be introduced. Their preparation, characterization, photophysical properties, electrochemical properties as well as the conformationally fluxional behavior in solution will be discussed, supported by computational studies. In the final chapter, synthesis and properties of mechanoresponsive polymers incorporating the copper(I)-pyridinophane-arylamide complexes as mechanophores will be presented. Optimization of the preparation method, photophysical properties and the mechanoresponsive properties of these polymers will be discussed.doctoral thesi