《从头算研究取代基效应对Os配合物结构和光谱性质的影响》-毕业学术论文设计.docVIP

PAGE 摘 要 理论研究了一系列[Os(II)(CO)3(tfa)(acac(X)2)] (tfa=trifluoroacetate; acac=acetoy lacetonate; X=H (1), CF3 (2), C6H5 (3), and C10H7 (4))配合物的几何和电子结构以及光谱特征。对基态和激发态几何的优化分别采用B3LYP/LANL2DZ和CIS/LANL2DZ方法，优化得到的几何参数和相应的实验值符合得很好，基态和激发态结构的些微不同对应着实验上观测到的较小的斯托克斯频移。 研究结果表明，配合物1和2的最高占据分子轨道(HOMO)主要由Os原子、ctfa(CO和tfa的加和)和acac配体共同占据，3和4的HOMO则定域在acac配体和X取代基上，而四个配合物的最低空轨道(LUMO)都是由acac配体和X取代基共同组成。在优化的基态和激发态结构的基础上，采用含时密度泛函理论方法(TD-DFT)联合极化连续溶剂化模型(PCM)，我们计算了它们在CH2Cl2溶液中的吸收和发射光谱。计算表明，1-4的最低能吸收分别位于317 (1), 342 (2), 377 (3)和420 nm (4)，它们属于ππ*/MLCT跃迁到纯的ππ*跃迁的转变，并且它们的磷光发射有相似的跃迁特征。 关键词：β-二酮锇配合物；电子结构；光谱性质；CIS方法 Abstract The geometries, electronic structures, and spectroscopic properties of a series of [Os(II)(CO)3(tfa)(acac(X)2)] (tfa=trifluoroacetate; acac=acetoylacetonate; X=H (1), CF3 (2), C6H5 (3), and C10H7 (4)) complexes have been investigated theoretically. The ground and excited states geometries were optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. The optimized geometry structural parameters were agree well with the corresponding experimental results. As indicated in paper, the highest occupied molecular orbitals (HOMO) were dominantly localized on the Os atom, ctfa (abbv. of CO and tfa), and acac ligand for 1 and 2, acac ligand and X substituent for 3 and 4, while the lowest unoccupied molecular orbitals (LUMO) were mainly composed of acac ligand and X substituent. Under the time-dependent density functional theory (TDDFT) level with the polarized continuum model (PCM), the absorption and phosphorescence in CH2Cl2 media were calculated based on the optimized ground- and excited-states geometries, respectively. The calculated results show that the lowest energy absorptions at 317 (1), 342 (2), 377 (3), and 420 nm (4) are attributed to a change of ππ*/MLCT HYPERLINK /dict_result.aspx?r=1t=mixing+transitionsearchword=%e6%b7%b7%e5%90%88%e8%b7%83%e8%bf%81 mixing transition to pure ππ* transition for 1-4, while their phosphorescence emission have similar transition