Synthesis And Materialization Studies Of 12C-Carbolong Complexes

Metallopolymers are a new type of multifunctional materials that have intrigued many scientists attention on them since the first metal-containing polymer,poly(vinylferrocene)was reported.In comparison to ultraviolet light or visible light,near-infrared(NIR)light shows many advantages such as deep penetration,low energy,less damage and so on.Therefore,the "near-infrared window" is also called the"biological window".NIR-responsive materials are widely used in photothermal therapy and photodynamic therapy.Carbolong complexes originally developed by our group are a series of functional molecules with novel structure and outstanding photoelectronic properties.The dissertation is devoted to introduce 12C "carbolong"complex into polymer systems to prepare functional polymer materials containing metalla-aramatic complex,and applications of that on stimulation response or smart materials are also explored.The research ideas of this paper are stated in the following five chapters.In chapter 1,combined with the study contents of this thesis,the synthetic methods and application of carbolong complexes,the development history and applications,the classification of NIR-absorbing materials and applications are briefly introduced.Besides,the conception and purpose of this paper are introduced in brief.In chapter 2,the reaction intermediates of 12C carbolong complex is explored.Treatment of cyclopropaosmapentalene with EtC=CEt gives a new type of polycyclic metalla-aromatic complex with a structure containing a ?-agostic Os H-C(sp3).When EtC?CCOMe is used,the reaction gives a more thermally stable ketone-coordinated complex and two products are obtained under different treatment conditions.The DFT study indicats that the difference between two reactions roots in the thermodynamic stability of the compounds.In chapter 3,a temperature-sensitive,corn-like cylindrical metallopoiymer with NIR-responsive is synthesized.Firstly,it is prepared from the controlled polymerization of N-isopropylacrylamide(NIPAM)by a polyrotaxane-based macroinitiator.Then a post-polymerization modified azide reacts with alkylnyl-12C carbolong complex to obtain metallopolymer.The corn-like shape of this metallopolymer is confirmed by transmission electron microscopy(TEM).Combining the photothermal effect of 12C carbolong complex unit and the thermosensitive property of PNIPAM,the corn-like metallopolymer exhibits NIR-responsive behavior,it can be regarded as a thermalsensitive and photosensitive smart material.In chapter 4,a NIR-rewritable and remendable thermosets containing metalla-aromatic complex is developed.The polyurethane thermosetting material based on dynamic covalent Diels-Alder(DA)network is introduced a novel photothermal reagent,12C carbolong complex.Under the NIR irradiation,the photothermal effect of 12C carbolong complex unit triggers the reversible Diles-Alders reaction,making the material shows the ability to repair cracks.Moreover,this material displays shape memory property,which can store information by modulating laser density to control the deformation behavior.In chapter 5,the research contents of this dissertation is totally summarized and the future work is prospected.