Synthesis And Optical Properties Of O-carborane Derivatives

The carborane dervatives with D-?-A structure have been attracted more and more attention in the fields of molecular batteries,nonlinear optics,optoelectronic materials because of its three-dimensional aromatic,unique physical and chemical properties and highly chemically thermal stability.This project based on ortho-carborane designed and synthesized a series of ortho-carborane dervatives and studied its unique optical properties.In summary,the work of this paper was mainly divided two parts: the studies of linear optics(especially solid photoluminescence)and the studies of nonlinear optics(this paper have finished the relevant synthesis and characterization work).In the second chapter,the solid fluorescence of the fluorenyl-tethered carborane dervatives(Fl-Cb)was studied.These compounds in both mono-aryl and di-aryl assemblies were synthesized from the alkyne and B10H12((C2H5)S)2 in yields around 60%.The crystallography in di-aryl analogues have shown successive/rigid packings in head-to-tail or tail-to-tail mode within both substituents attached,while in the mono-aryl analogues,only flabby packing was observed.In the solution,Fl-Cb compounds have exhibited severe quenching in their emission,and the aggregation in a mixed solvent achieved an ehancement emission with 0.11 quantum efficiency.Neverthelss,crystallization induced emission was observed in the di-aryl analogues with quantum efficiency up to 0.95.Other than the broad emission spectra,the excitation spectra in these analogues was also broadened which implies considerable orbital degeneracy within the crystals.As corroborated by theoretical calculations,the inherent orbital degeneracy,in combination with the highly-ordered crystalline aggregates,attribtuted to the excellent crystallization induced emission in Fl-Cb compounds.In the third chapter,the preliminary synthesis work of the carborane dervatives in the field of the three-order nonlinear optics was mainly studied.A series of carborane dervatives with “Z” structure,including c1,c2,c3,c4 and c5 which contain different electronic-donating moieties,have been prepared through Sornogashira coupling reaction,et al.The molecular of all the compounds have run NMR,MS,FT-IR,EA and the accurancy of these compounds were also confirmed by these tests.