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具有光物理惰性硼簇配体的发光金属配合物。

Luminescent Metal Complexes Featuring Photophysically Innocent Boron Cluster Ligands.

作者信息

Kirlikovali Kent O, Axtell Jonathan C, Gonzalez Alejandra, Phung Alice C, Khan Saeed I, Spokoyny Alexander M

机构信息

Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, California 90025-1569, USA.

出版信息

Chem Sci. 2016 Aug 1;7(8):5132-5138. doi: 10.1039/C6SC01146B. Epub 2016 Apr 27.

DOI:10.1039/C6SC01146B
PMID:28191302
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5300762/
Abstract

We report the synthesis and characterization of a series of d metal complexes featuring robust and photophysically innocent strong-field chelating 1,1'-bis(-carborane) () ligand frameworks. A combination of UV-Vis spectroscopy, single crystal X-ray structural analysis, and DFT calculations of these species suggest that the dianionic ligand does not contribute to any visible metal-to-ligand charge transfer (MLCT) transitions, yet it provides a strong ligand field in these complexes. Furthermore, a -based Pt(II) complex containing a 4,4'-di--butyl-2,2'-bipyridine ligand (dtb-bpy) has been prepared and was found to display blue phosphorescent emission dominated by MLCT from the Pt(II) center to the dtb-bpy ligand. Importantly, the bulky three-dimensional nature of the ligand precludes intermolecular Pt(II)⋯Pt(II) interactions in the solid state where the resulting compounds retain their emission properties. This study opens a potentially new avenue for designing organic light-emitting diode (OLED) materials with tunable properties featuring photophysically innocent boron-rich cluster ligands.

摘要

我们报道了一系列具有稳定且光物理性质惰性的强场螯合1,1'-双（-碳硼烷）（）配体骨架的d金属配合物的合成与表征。对这些物质进行紫外-可见光谱、单晶X射线结构分析和密度泛函理论计算相结合的研究表明，二价阴离子配体对任何可见的金属到配体的电荷转移（MLCT）跃迁均无贡献，但它在这些配合物中提供了强配体场。此外，已制备出一种含有4,4'-二-丁基-2,2'-联吡啶配体（dtb-bpy）的基于的Pt(II)配合物，发现其显示出以从Pt(II)中心到dtb-bpy配体的MLCT为主的蓝色磷光发射。重要的是，配体的庞大三维性质排除了固态中分子间Pt(II)⋯Pt(II)相互作用，所得化合物在固态时保留其发射性质。这项研究为设计具有可调性质且以光物理性质惰性的富硼簇配体为特征的有机发光二极管（OLED）材料开辟了一条潜在的新途径。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/4b691e7497c1/c6sc01146b-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/d491c44a649c/c6sc01146b-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/70942d753f51/c6sc01146b-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/28194b1c33d2/c6sc01146b-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/fe5fd27d4d11/c6sc01146b-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/9aef785a47dd/c6sc01146b-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/4b691e7497c1/c6sc01146b-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/d491c44a649c/c6sc01146b-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/70942d753f51/c6sc01146b-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/28194b1c33d2/c6sc01146b-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/fe5fd27d4d11/c6sc01146b-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/9aef785a47dd/c6sc01146b-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cc90/6020124/4b691e7497c1/c6sc01146b-f6.jpg

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