Featuring a new computational protocol for the estimation of intensity and overall quantum yield in lanthanide chelates with applications to Eu(III) mercapto-triazole Schiff base ligands
Featuring a new computational protocol for the estimation of intensity and overall quantum yield in lanthanide chelates with applications to Eu(III) mercapto-triazole Schiff base ligands
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DOI：
10.1016/j.omx.2022.100216
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发表时间：
2022-11
影响因子：
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通讯作者：
Renaldo T. Moura Jr.;Mateus M. Quintano;Carlos V. Santos-Jr.;Vinícius A.C.A. Albuquerque;E. C. Aguiar
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文献类型：
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作者：
Renaldo T. Moura Jr.;Mateus M. Quintano;Carlos V. Santos-Jr.;Vinícius A.C.A. Albuquerque;E. C. Aguiar
镧系元素螯合物发光性质的计算研究对于新型发光材料的预合成设计具有重要意义。然而，合适的计算方法和协议的发展仍处于起步阶段。在这里，我们提出了一个新的计算协议的Ln（III）螯合物的发光特性的系统描述和分析。本文提出的新方法分为三大类：（1）利用局部振动模式理论获得本地Ln-配位体力常数;（2）通过复杂的本地化分子轨道计算配位体的有效极化率;（3）激发态施主-受体RL距离的扩展配方占激发分子轨道重量。利用含时密度泛函理论（ω B 97 X-D/MWB 52（Eu）/Def 2-TZVP）研究了两种以巯基三唑Schiff碱为主要配体的Eu（III）配合物的电子物理过程.局域力常数的引入导致镧系元素光谱的一个独特的解释之间的反比关系的Ln-配体的强度和配体的有效极化率。这种新的协议将有助于更好地理解Ln-配体键的性质，更准确的结果在Judd-Ofelt强度参数和整体量子产率方面，并将弥合现有的理论结果和实验数据之间的差距。
Computational studies on luminescent properties of lanthanides chelates are important for the pre-synthetic design of new luminescent materials. However, the development of suited computational methods and protocols is still in its infancy. Here we present a new computational protocol for a systematic description and analysis of luminescent properties of Ln (III) chelates. The new methodologies herein presented are divided in three major categories:(1) Utilization of local vibrational mode theory for obtaining local Ln–ligand force constants;(2) Calculation of ligand effective polarizabilities through complex localized molecular orbitals; and (3) Extended formulation of excited state donor–acceptor R L distances accounting for excited molecular orbitals weights. The protocol was applied to understand the underlying photophysical processes in two Eu (III) complexes with mercapto-triazole Schiff bases as main ligands, utilizing time-dependent density functional theory (ω B97X-D/MWB52 (Eu)/Def2-TZVP). The introduction of local force constants into lanthanide spectroscopy led to a unique explanation of the inverse relationship between the Ln–ligand strength and ligand effective polarizability. This new protocol will contribute to a better understanding of Ln–ligand bond properties, to more accurate results in terms of Judd–Ofelt intensity parameters and overall quantum yield, and will bridge the current gap between available theoretical results and experimental data.