有机化学 ›› 2018, Vol. 38 ›› Issue (1): 171-182.DOI: 10.6023/cjoc201709010 上一篇    下一篇

所属专题: 庆祝吴养洁院士九十华诞专辑

研究论文

基于C^N^N三齿配体以及苯乙炔基或苯基的环金属化铂磷光络合物的比较研究

Robert Mroza, Dileep A. K. Vezzua, Brian Wallacea, Deepak Ravindranathana, Jeffrey Carrolla, Robert D. Pikeb, 霍守权a   

  1. a Department of Chemistry,East Carolina University, Greenville, North Carolina 27858, USA;
    b Department of Chemistry, College of William and Mary, Williamsburg, VA 23185, USA
  • 收稿日期:2017-09-08 修回日期:2017-10-12 出版日期:2018-01-25 发布日期:2017-10-16
  • 通讯作者: 霍守权 E-mail:huos@ecu.edu

A Comparative Study on Phosphorescent Cycloplatinated Complexes Based on Tridentate C^N^N-Coordinating Ligands and Phenylethynyl or Phenyl Ligand

Mroz Roberta, Vezzu Dileep A. K.a, Wallace Briana, Ravindranathan Deepaka, Carroll Jeffreya, Pike Robert D.b, Huo Shouquana   

  1. a Department of Chemistry, East Carolina University, Greenville, North Carolina 27858, USA;
    b Department of Chemistry, College of William and Mary, Williamsburg, VA 23185, USA
  • Received:2017-09-08 Revised:2017-10-12 Online:2018-01-25 Published:2017-10-16
  • Contact: 霍守权 E-mail:huos@ecu.edu

合成了两个系列的以2-芳基-6-(1H-砒唑-1-基)砒啶[芳基=苯基(L1),2,4-二氟苯基(L2),3,5-二甲基苯(L3),3-甲氧基苯基(L4),2-噻吩基(L5),2-苯并噻吩基(L6)]为环金属化配体,以苯乙炔基或苯基为辅助配体的铂化合物1a6a1b6b.其中2b3b5b的结构用X射线晶体衍射方法进行了测定.结果表明,辅助基团苯基与配位平面采取一种扭曲的构型.Pt—C(苯基)键较Pt—C(炔基)键弱.对铂化合物的光物理性质包括吸收和发射光谱进行了研究.苯乙炔基取代的铂化合物1a6a在室温溶液里发射较强的磷光,而苯基取代的确铂化合物1b3b仅发射很弱的光.但是,化合物4b6b发射比较强的光,尽管发光效率还是比相应的4a6a低.这一现象表明4b6b4a6a的激发态可能定域在三齿环金属化配体上.化合物1a6a表现的较高发光效率可能是因为较强的和刚性的炔基配体.

关键词: 铂络合物, 磷光材料, 晶体结构, 光物理

Two series of platinum complexes, 1a6a and 1b-6b, based on tridentate cyclometalating ligands 2-aryl-6-(1H- pyrazol-1-yl)pyridine [Ar=phenyl (L1), 2,4-difluorophenyl (L2), 3,5-dimethylphenyl (L3), 3-methoxyphenyl (L4), 2-thienyl (L5), 2-benzothienyl (L6)], and phenylethynyl and phenyl ancillary ligand were synthesized and characterized. The X-ray crystal structures of 2b, 3b and 5b were determined, which revealed a twisted orientation of the phenyl ligand with respect to the coordination plane and a weaker Pt—C(phenyl) bond compared with the Pt—C(alkynyl) bond in 1a. Photophysical properties including electronic absorption and emission spectra were studied. Complexes 1a6a based on the phenylethynyl ligand were strongly emissive, while 1b3b based on the phenyl ligand were only weakly emissive. However, 4b6b displayed lower but decent photoluminescent quantum yields than those of 4a6a, which is explained by the localization of the excited states in the tridentate cyclometalating ligands. The higher quantum efficiencies displayed by the complexes 1a6a may be attributed to the stronger and more rigid acetylide ligand.

Key words: platinum complexes, phosphorescent materials, crystal structure, photophysics