Os(II) phosphors with near-infrared emission induced by ligand-to-ligand charge transfer transition.
Os(II) phosphors with near-infrared emission induced by ligand-to-ligand charge transfer transition.
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DOI：
10.1021/ic501474r
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发表时间：
2014-08
影响因子：
4.6
通讯作者：
Jia‐Ling Liao;Y. Chi;Shih‐Hung Liu;Gene-Hsiang Lee;P. Chou;Hao Huang;Yu-De Su;Chih‐Hao Chang
中科院分区：
文献类型：
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作者：
Jia‐Ling Liao;Y. Chi;Shih‐Hung Liu;Gene-Hsiang Lee;P. Chou;Hao Huang;Yu-De Su;Chih‐Hao Chang
Os3（CO）12与6当量的2-（3-（三氟甲基）-1H-1，2，4-三唑-5-基）吡啶（fptzH）在回流的二乙二醇单甲基醚中，随后用化学计量的Me 3 NO顺序处理并添加PPhMe 2，得到两种发红色的异构体混合物[Os（fptz）2（PPhMe 2）2]（1 T和1C），其中符号T和C分别代表反式和顺式取向的fptz螯合物。或者，使用5，5 '-二（三氟甲基）-3，3'-二-1，2，4-三唑（dttzH 2）和2，2 '-联吡啶（bpy）的1：1混合物代替fptzH制备Os（II）络合物，以中等产率分离单核Os（II）络合物[Os（bpy）（dttz）（CO）2]（2）。用PPhMe 2取代CO得到了具有近红外（NIR）发射的Os（II）配合物[Os（bpy）（dttz）（PPhMe 2）2]（3）。对1C、2和3进行单晶X射线结构分析，以揭示各种螯合物对结构的影响。利用密度泛函理论（DFT）和含时DFT计算的结果，测量和讨论的物理和电化学性质。选择配合物3作为掺杂剂，通过制备发射近红外光的有机电致发光二极管来研究其电致发光性质。
Heating of Os3(CO)12 with 6 equiv of 2-(3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl) pyridine (fptzH) in refluxing diethylene glycol monomethyl ether, followed by sequential treatment with stoichiometric Me3NO and addition of PPhMe2, afforded two isomeric mixtures of red-emitting [Os(fptz)2(PPhMe2)2] (1T and 1C), for which the notations T and C stand for the trans and cis-oriented fptz chelates, respectively. Alternatively, preparation of Os(II) complex using a 1:1 mixture of 5,5'-di(trifluoromethyl)-3,3'-di-1,2,4-triazole (dttzH2) and 2,2'-bipyridine (bpy), instead of fptzH, gave isolation of a mononuclear Os(II) complex [Os(bpy)(dttz)(CO)2] (2) in moderate yield. Replacement of CO with PPhMe2 on 2 afforded near-infrared (NIR)-emitting Os(II) complex [Os(bpy)(dttz)(PPhMe2)2] (3). The single-crystal X-ray structural analyses were executed on 1C, 2, and 3 to reveal the structural influence imposed by the various chelates. The photophysical and electrochemical properties were measured and discussed using the results of density functional theory (DFT) and time-dependent DFT calculations. Complex 3 is selected as the dopant to probe its electroluminescent properties by fabrication of the NIR emitting organic light-emitting diodes.