Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties.
Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties.
复制标题
DOI：
10.1021/acs.inorgchem.3c03290
复制
发表时间：
2024-01-08
影响因子：
4.6
通讯作者：
Schroeder, Bob C.
中科院分区：
文献类型：
--
作者：
Bhatia, Harsh;Guo, Junjun;Savory, Christopher N.;Rush, Martyn;James, David Ian;Dey, Avishek;Chen, Charles;Bucar, Dejan-Kresimir;Clarke, Tracey M.;Scanlon, David O.;Palgrave, Robert G.;Schroeder, Bob C.
铋基配合物优于其他金属配合物，因为铋是最重的无毒元素，具有高自旋轨道耦合和潜在的光电子应用。本文合成了四种卤化铋基配合物[Bi2Cl6(pheno -thio)2](1)、[Bi2Br6(pheno -thio)2](2)、[Bi2I6(pheno -thio)2](3)和[Bi2I6(phene - me)2](4)，并对其进行了详细的光物理研究。通过单晶x射线衍射、粉末x射线衍射和核磁共振研究对配合物进行了表征。在不同极性溶液中对1-4进行光谱分析，以了解有机和无机组分在确定配合物基态和激发态性质中的作用。通过基态吸收、稳态光致发光、微秒时间分辨光致发光和吸收光谱对配合物的光物理性质进行了表征。利用周期密度泛函理论（DFT）对固体结构进行了计算，以了解配合物中有机和无机部分的作用。研究表明，将氯（Cl）和溴（Br）的辅助配体改为碘(I)会使吸收带发生色移，吸收系数增大。此外，改变卤化物（Cl, Br to I）会影响配体中心（LC）发射态的光致发光量子产率，但不会显著影响寿命。综合结果证实，基态性质受到无机部分的强烈影响，低能激发态为LC。本研究通过对配体和铋盐的严格选择，为设计新型光电配位配合物铺平了道路。我们合成了四种新的卤化铋配位配合物，表明改变辅助配体不仅会改变吸收带，而且会影响配体中心发射态的光致发光量子产率，而不会显著影响寿命。这证实了无机组分对基态性质的强烈影响，其中能量较低的激发态是配体中心的。这表明，通过仔细选择配体和铋盐，可以设计用于光电应用的新型铋配位配合物。
Bismuth-based coordination complexes are advantageous over other metal complexes, as bismuth is the heaviest nontoxic element with high spin–orbit coupling and potential optoelectronics applications. Herein, four bismuth halide-based coordination complexes [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio)2] (2), [Bi2I6(phen-thio)2] (3), and [Bi2I6(phen-Me)2] (4) were synthesized, characterized, and subjected to detailed photophysical studies. The complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and NMR studies. Spectroscopic analyses of 1–4 in solutions of different polarities were performed to understand the role of the organic and inorganic components in determining the ground- and excited-state properties of the complexes. The photophysical properties of the complexes were characterized by ground-state absorption, steady-state photoluminescence, microsecond time-resolved photoluminescence, and absorption spectroscopy. Periodic density functional theory (DFT) calculations were performed on the solid-state structures to understand the role of the organic and inorganic parts of the complexes. The studies showed that changing the ancillary ligand from chlorine (Cl) and bromine (Br) to iodine (I) bathochromically shifts the absorption band along with enhancing the absorption coefficient. Also, changing the halides (Cl, Br to I) affects the photoluminescent quantum yields of the ligand-centered (LC) emissive state without markedly affecting the lifetimes. The combined results confirmed that ground-state properties are strongly influenced by the inorganic part, and the lower-energy excited state is LC. This study paves the way to design novel bismuth coordination complexes for optoelectronic applications by rigorously choosing the ligands and bismuth salt. We synthesized four new Bismuth halide-based coordination complexes revealing that altering the ancillary ligand not only shifts the absorption band, but also impacts photoluminescent quantum yields of the ligand-centered emissive state without significantly affecting lifetimes. This confirms the strong influence of the inorganic component on ground state properties, with the lower energy excited state being ligand-centered. This suggests opportunities for designing novel Bismuth coordination complexes for optoelectronic applications by carefully selecting ligands and Bismuth salts.
登录
查看更多内容
影响因子：
6.1
作者：
Hübschle CB;Sheldrick GM;Dittrich B
通讯作者：
Dittrich B
影响因子：
2.3
作者：
Adcock, Alyssa K.;Batrice, Rami J.;Knope, Karah E.
通讯作者：
Knope, Karah E.
影响因子：
3.7
作者：
Kresse, G;Furthmuller, J
通讯作者：
Furthmuller, J
影响因子：
3
作者：
Grimme, S
通讯作者：
Grimme, S
影响因子：
2.8
作者：
Horváth, O;Mikó, I
通讯作者：
Mikó, I