Impact of a Picolinate Ancillary Ligand on Phosphorescence and Fluoride Sensing Properties of BMes2-Functionalized Platinum(II) Compounds

详细信息    查看全文

• 作者：Soo-Byung Ko ; Jia-Sheng Lu ; Youngjin Kang ; Suning Wang
• 刊名：Organometallics
• 出版年：2013
• 出版时间：January 28, 2013
• 年：2013
• 卷：32
• 期：2
• 页码：599-608
• 全文大小：604K
• 年卷期：v.32,no.2(January 28, 2013)
• ISSN：1520-6041

文摘

Two new dimesitylboron (BMes₂)-functionalized 2-phenylpyridine cyclometalated Pt(II) complexes (2 and 3) with a picolinate or a methyl-picolinate as the ancillary ligand have been synthesized via a one-pot procedure at ambient conditions with high yields (>70%). The crystal structures of these Pt(II) complexes were determined by single-crystal X-ray diffraction analysis, which revealed the presence of extended 蟺-stacking interactions in the crystal lattice of 2 and discrete dimer formation in the lattice of 3. Both complexes exhibit dual phosphorescence emission in solution at room temperature under N₂ atmosphere. These unusual photophysical properties have been systematically investigated by spectroscopic and computational studies, which established that the phosphorescent dual emission originates from admixture of ³LLCT and ³ILCT/³MLCT transitions. Fluoride titration experiments were conducted to further confirm the origin of phosphorescence in these compounds. The phosphorescent properties and the phosphorescent response toward fluoride ions by compounds 2 and 3 are distinctly different from the previously known BMes₂-functionalized NC-chelate Pt(II) compounds, which are attributed to the introduction of the low-lying 蟺* orbital by the picolinate ancillary ligand in the Pt(II) compounds.