苯甲酸衍生物的Tb(Ⅲ)配合物中配体电子结构对Tb^3+的f→f超灵敏跃迁的影响  

Effects of Ligands' Electronic Structures on the Hypersensitives f→f Transitions of a Series of Complexes of Tb(Ⅲ) With Substituted Benzoic Acid

作　　者：张干兵[1] 胡林学[1] 李建平[1] 宋功武[1] 

机构地区：[1]湖北大学化学与材料科学学院,湖北武汉430062

出　　处：《湖北大学学报（自然科学版）》1999年第4期361-364,共4页Journal of Hubei University：Natural Science

基　　金：湖北大学青年基金

摘　　要：用HMO分子轨道法对6个苯甲酸衍生物RC6H4CO2H（R＝o－NH2、H、p－NH2、o－OH、m－Cl、o－COOH）作了半经验量子化学计算．逐步回归的结果表明，该6个化合物与钛Tb（Ⅲ）的二元配合物在紫外光激发下的荧光光谱中，标志Tb3+的超灵敏跃迁强度的量：蓝光（491nm）与绿光（545nm）的相对强度比（IB/G）与配体的前线轨道能量（EHOMO和ELUMO）、共振能ER及羟基氧的亲电前线电行密度FE（O1）或羟基氧和碳基氧的亲电前沿电荷密度之和FE（O1＋O2）等量化指标之间有很好的相关性．定量地探讨了其结构与性能的关系，为进一步探索该类新型绿色发光材料及深化对镧系离子超灵敏跃迁的认识有一定的意义．Quantitative studies were reported on the fluorescence properties and electronic structures of a series of complexes of Tb(Ⅲ) with substituted benzoic acid RC6H4CO2H(R = o-NH2,H,p - NH2, o - OH, m-Cl, o-COOH),by means of fluorescence spectra, quantum chemical HMO theory and stepwise multivariable regression metheds. The results showed that the hypersensitive transition intensity ratio (IB/G ) is well correated with ligand's HM0 indexes: the resonance eneng ER, the energy level of the highest occupied edular othital (EHOMO ) or that of the lowest unoccupied moecular orbital (ELUMO ) and the electrophilic frontier electron density of hydroxyl oxygen FE(O1 ) or the sum of hydroxyl oxygen and carbol oxygen FE(O1 + O2 ). In two of these quantitativ relationships, the cormlation coefficients are more than 0. 99, and the standaxd devibo axe less than 0. 01.The results can be satisfactorily ratiednd with Masson's ligand pezation theory.

关 键 词：苯甲酸衍生物 铽 配合物 配体 电子结构 

分 类 号：O614.341[理学—无机化学]