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题名: Tuning the emission properties of cyclometalated platinum(II) complexes by intramolecular electron-sink/arylethynylated ligands and its application for enhanced luminescent oxygen sensing
作者: Wu, Wanhua1;  Wu, Wenting1;  Ji, Shaomin1;  Guo, Huimin2;  Song, Peng3;  Han, Keli3;  Chi, Lina1;  Shao, Jingyin1;  Zhao, Jianzhang1
刊名: JOURNAL OF MATERIALS CHEMISTRY
发表日期: 2010
DOI: 10.1039/c0jm01794a
卷: 20, 期:43, 页:9775-9786
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences ;  Technology
类目[WOS]: Chemistry, Physical ;  Materials Science, Multidisciplinary
研究领域[WOS]: Chemistry ;  Materials Science
英文摘要: We have synthesized five novel cyclometalated Pt(II) complexes (aryl-ppy)Pt(acac) (ppy = 2-phenyl pyridine, aryl N-butyl naphthalimide (NI) ethynylene for Pt-1, N-butyl naphthalimide (NI)-CH(2) CO for Pt-2, 4-cyanophenyl CH(2) CO for Pt-3, naphthal ethynylene for Pt-4 and naphthal-diketo for Pt-5). For the first time, pi-conjugation of the ppy ligands was extended via the C C bond. Deep red/near IR emission (638 nm-700 nm) was observed for the complex containing naphthalimide ethynylene subunit (Pt-1), whereas the close analogue Pt-2 (in which the linker between the NI and the ppy subunit is a -CH(2)CO- group) shows a relatively blue-shifted emission (540 nm-570 nm) but much longer luminescent lifetime (tau = 25.5 mu s) than Pt-1 (tau = 6.6 mu s). Simultaneous fluorescence/phosphorescence emissions were observed for Pt-1 and Pt-2, but other complexes show sole phosphorescent emission. The red-shifted phosphorescence of the complexes compared to the model complex ppyPt(acac) (486 nm) was attributed to either the significant electron-sink effect of the NI fragment (Pt-1) (for which the electron withdrawing effect is stronger than the previously reported fluoren-9-one), or the extended pi-conjugation of the ppy ligand (via C C bond) (e. g. Pt-4). The substantial tuning of the emission color and the luminescent lifetimes (0.86 mu s-25.5 mu s) of the complexes were rationalized by theoretical calculations (DFT/TDDFT), i.e. the emissive triplet excited states were assigned as the normal (3)MLCT state (give smaller tau values) or the novel ligand-localized (3)IL emissive state (give larger tau values). With tuning the luminescent lifetimes, the luminescent O(2) sensitivity of the complexes was improved by 117-fold (Stern-Volmer quenching constants K(SV) = 0.234 Torr(-1) for Pt-2 vs. K(SV) = 0.002 Torr(-1) for Pt-5).
关键词[WOS]: PHOTOPHYSICAL PROPERTIES ;  TRIPLET EMITTERS ;  EXCITED-STATE ;  ACETYLIDE CHROMOPHORES ;  MESOPOROUS SILICA ;  OLED APPLICATIONS ;  WHITE-LIGHT ;  FLUORESCENT ;  SENSORS ;  PROBE
语种: 英语
WOS记录号: WOS:000283603000028
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142010
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Dalian Univ Technol, State Key Lab Fine Chem, Sch Chem Engn, Dalian 116012, Peoples R China
2.Dalian Univ Technol, Dept Chem, Sch Chem Engn, Dalian 116012, Peoples R China
3.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China

Recommended Citation:
Wu, Wanhua,Wu, Wenting,Ji, Shaomin,et al. Tuning the emission properties of cyclometalated platinum(II) complexes by intramolecular electron-sink/arylethynylated ligands and its application for enhanced luminescent oxygen sensing[J]. JOURNAL OF MATERIALS CHEMISTRY,2010,20(43):9775-9786.
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