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Theoretical Modeling (Sparkle RM1 and PM7) and Crystal Structures of the Luminescent Dinuclear Sm(III) and Eu(III) Complexes of 6,6,7,7,8,8,8- Heptafluoro-2,2-dimethyl-3,5-octanedione and 2,3-Bis(2-pyridyl)pyrazine: Determination of Individual Spectroscopic Parameters for Two Unique Eu3+ Sites
ACS Omega ( IF 3.7 ) Pub Date : 2021-08-11 , DOI: 10.1021/acsomega.0c05976
Aabid Bashir Ganaie 1 , Khalid Iftikhar 1
ACS Omega ( IF 3.7 ) Pub Date : 2021-08-11 , DOI: 10.1021/acsomega.0c05976
Aabid Bashir Ganaie 1 , Khalid Iftikhar 1
Affiliation
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Heteroleptic homo dinuclear complexes [Sm(fod)3(μ-bpp)Sm(fod)3] and [Eu(fod)3(μ-bpp)Eu(fod)3] and their diamagnetic analogue [Lu(fod)3(μ-bpp)Lu(fod)3] (fod is the anion of 6,6,7,7,8,8,8- heptafluoro-2,2-dimethyl-3,5-octanedione (Hfod) and bpp is 2,3-bis(2-pyridyl)pyrazine) are synthesized and thoroughly characterized. The lanthanum gave a 1:1 adduct of La(fod)3 and bpp with the molecular formula of [La(fod)3bpp]. The 1H NMR and 1H-1H COSY spectra of the complexes were used to assign the proton resonances. In the case of paramagnetic Sm3+ and Eu3+ complexes, the methine (of the fod moiety) and the bpp resonances are shifted in the opposite direction and the paramagnetic shifts are dipolar in nature, which decrease with increasing distance of the proton from the metal ion. The single-crystal X-ray analyses reveal that the complexes (Sm3+ and Eu3+) are dinuclear and crystallize in the triclinic P1 space group. Each metal in a given complex is eight coordinate by coordinating with six oxygen atoms of three fod moieties and two nitrogen atoms of the bpp. Of the two metal centers, in a given complex, one has a distorted square antiprism arrangement and the other acquires a distorted dodecahedron geometry. The Sparkle RM1 and PM7 optimized structures of the complexes are also presented and compared with the crystal structure. Theoretically observed bond distances are in excellent agreement with the experimental values, and the RMS deviations for the optimized structures are 2.878, 2.217, 2.564, and 2.675 Å. The photophysical properties of Sm3+ and Eu3+ complexes are investigated in different solvents, solid, and PMMA-doped thin hybrid films. The spectroscopic parameters (the Judd–Ofelt intensity parameters, radiative parameters, and intrinsic quantum yield) of each Eu3+ sites are calculated using the overlap polyhedra method. The theoretically obtained parameters are close to the experimental results. The lifetime of the excited state is 38.74 μs for Sm3+ and 713.62 μs for the Eu3+ complex in the solid state.
中文翻译:
6,6,7,7,8,8,8-七氟-2,2-二甲基-3的发光双核Sm(III)和Eu(III)配合物的理论建模(Sparkle RM1和PM7)和晶体结构, 5-辛二酮和 2,3-双(2-吡啶基)吡嗪:确定两个独特的 Eu3+ 位点的单独光谱参数
杂配的同源双核复合物[Sm(fod) 3 (μ-bpp)Sm(fod) 3 ]和[Eu(fod) 3 (μ-bpp)Eu(fod) 3 ]及其抗磁性类似物[Lu(fod) 3 ( μ-bpp)Lu(fod) 3 ](fod是6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5-辛二酮(Hfod)的阴离子,bpp是2 ,3-双(2-吡啶基)吡嗪)被合成并彻底表征。镧产生 La(fod) 3和 bpp的 1:1 加合物,分子式为 [La(fod) 3 bpp]。复合物的1 H NMR 和1 H- 1 H COZY 光谱用于指定质子共振。在顺磁性 Sm 3+的情况下和 Eu 3+配合物、次甲基(fod 部分)和 bpp 共振向相反方向移动,顺磁移动本质上是偶极的,随着质子与金属离子距离的增加而减小。单晶X射线分析表明配合物(Sm 3+和Eu 3+)是双核的并在三斜P中结晶1个空间群。通过与三个 fod 部分的六个氧原子和 bpp 的两个氮原子配位,给定复合物中的每种金属是八个配位。在两个金属中心中,在给定的复合物中,一个具有扭曲的方形反棱镜排列,另一个获得扭曲的十二面体几何形状。还展示了配合物的 Sparkle RM1 和 PM7 优化结构,并与晶体结构进行了比较。理论上观察到的键距与实验值非常吻合,优化结构的 RMS 偏差为 2.878、2.217、2.564 和 2.675 Å。Sm 3+和Eu 3+的光物理性质在不同的溶剂、固体和 PMMA 掺杂的混合薄膜中研究了复合物。使用重叠多面体方法计算每个 Eu 3+位点的光谱参数(Judd-Ofelt 强度参数、辐射参数和本征量子产率)。理论得到的参数与实验结果接近。Sm 3+的激发态寿命为38.74 μs,固态的Eu 3+ 配合物为713.62 μs 。
更新日期:2021-08-24
中文翻译:
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6,6,7,7,8,8,8-七氟-2,2-二甲基-3的发光双核Sm(III)和Eu(III)配合物的理论建模(Sparkle RM1和PM7)和晶体结构, 5-辛二酮和 2,3-双(2-吡啶基)吡嗪:确定两个独特的 Eu3+ 位点的单独光谱参数
杂配的同源双核复合物[Sm(fod) 3 (μ-bpp)Sm(fod) 3 ]和[Eu(fod) 3 (μ-bpp)Eu(fod) 3 ]及其抗磁性类似物[Lu(fod) 3 ( μ-bpp)Lu(fod) 3 ](fod是6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5-辛二酮(Hfod)的阴离子,bpp是2 ,3-双(2-吡啶基)吡嗪)被合成并彻底表征。镧产生 La(fod) 3和 bpp的 1:1 加合物,分子式为 [La(fod) 3 bpp]。复合物的1 H NMR 和1 H- 1 H COZY 光谱用于指定质子共振。在顺磁性 Sm 3+的情况下和 Eu 3+配合物、次甲基(fod 部分)和 bpp 共振向相反方向移动,顺磁移动本质上是偶极的,随着质子与金属离子距离的增加而减小。单晶X射线分析表明配合物(Sm 3+和Eu 3+)是双核的并在三斜P中结晶1个空间群。通过与三个 fod 部分的六个氧原子和 bpp 的两个氮原子配位,给定复合物中的每种金属是八个配位。在两个金属中心中,在给定的复合物中,一个具有扭曲的方形反棱镜排列,另一个获得扭曲的十二面体几何形状。还展示了配合物的 Sparkle RM1 和 PM7 优化结构,并与晶体结构进行了比较。理论上观察到的键距与实验值非常吻合,优化结构的 RMS 偏差为 2.878、2.217、2.564 和 2.675 Å。Sm 3+和Eu 3+的光物理性质在不同的溶剂、固体和 PMMA 掺杂的混合薄膜中研究了复合物。使用重叠多面体方法计算每个 Eu 3+位点的光谱参数(Judd-Ofelt 强度参数、辐射参数和本征量子产率)。理论得到的参数与实验结果接近。Sm 3+的激发态寿命为38.74 μs,固态的Eu 3+ 配合物为713.62 μs 。