二茂铁基查尔酮衍生物的超快三阶非线性光学响应

Ultrafast Third-Order Nonlinear Optical Response of Ferrocene-Based Chalcone Derivatives

合成三例二茂铁基查尔酮衍生物:1-二茂铁基-3-(5-溴噻吩-2-基)-2-丙烯-1-酮(1)、1-二茂铁基-3-(4-溴噻吩-2-基)-2-丙烯-1-酮(2)和1-二茂铁基-3-(5-氯噻吩-2-基)-2-丙烯-1-酮(3);采用1H NMR、13C NMR和HR-MS对化合物1~3进行了结构表征,并测定了其热学性质;运用密度泛函理论方法进行结构优化,并计算得到了它们的分子轨道能量和极化率;采用紫外-可见吸收光谱与Z-扫描技术(532nm,180fs)分别测定了三种化合物的线性和非线性光学性质。结果表明,化合物1~3的紫外吸收波长发生明显红移,且1的非线性吸收幅度、极化率和分子超极化率最大;1、2和3均存在分子内电荷转移现象,表现出超快三阶非线性光学响应。

Three novel chalcone derivatives of ferrocenyl,1-ferrocenyl-3-( 5-Bromothiophen-2-yl)-2-propen-1-one( 1),1-ferrocenyl-3-( 4-bromothiophen-2-yl)-2-propen-1-one( 2) and 1-ferrocenyl-3-( 5-chlorthiophen-2-yl)-2-propen-1-one( 3) were synthesized and characterized by1 H NMR,13 C NMR and HR-MS. The thermal properties of compounds 1 ~ 3 were measured. Their molecular orbital energies and polarizabilities were calculated by density functional theory method,and then the electronic cloud figures of the molecular orbitals were obtained. Their linear and nonlinear optical properties were investigated using UV-Vis absorption spectra and Z-scan technique( 532 nm,180 fs),respectively. The maximum absorption wavelength of compounds 1 ~ 3 increases significantly,and the nonlinear absorption amplitude,polarizability and molecular hyperpolarizability of compound 1 is the largest one.There is distinct intramolecular charge transfer phenomenon within these compounds,which results to interesting ultrafast third-order nonlinear optical response.