Sensitization of NIR Lanthanide Luminescence by Heteronuclear Platinum-Silver (Gold) Complexes with Ethynyl-Functionalized 2,2’：6’,2

doi:10.6023/A14030217

Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (6): 667-672.DOI: 10.6023/A14030217 Previous Articles Next Articles

Article

乙炔功能化2,2’：6’,2"-三联吡啶异三核铂-银(金)配合物敏化稀土近红外发光

徐广涛, 李佳, 陈忠宁

中国科学院福建物质结构研究所结构化学国家重点实验室福州福建 350002

投稿日期:2014-03-24 发布日期:2014-05-28
通讯作者: 陈忠宁 E-mail:czn@fjirsm.ac.cn
基金资助:
项目受国家自然科学基金（No.91122006）和福建省自然科学基金（No.2011J01065）资助.

Sensitization of NIR Lanthanide Luminescence by Heteronuclear Platinum-Silver (Gold) Complexes with Ethynyl-Functionalized 2,2’：6’,2"-Terpyridine

Xu Guangtao, Li Jia, Chen Zhongning

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

Received:2014-03-24 Published:2014-05-28
Supported by:
Supporting information for this article is available free of charge via the Internet at http://sioc-journal.cn.Project supported by the National Natural Science Foundation of China (No.91122006) and Natural Science Foundation of Fujian Province (No.2011J01065).

1. Sensitization of NIR Lanthanide Luminescence by Heteronuclear Platinum-Silver (Gold) Complexes with Ethynyl-Functionalized 2,2’：6’,2"-Terpyridine.PDF(540KB)

Abstract

With two highly phosphorescent heterotrinuclear complexes [PtM₂(dpmp)₂(C≡CC₆H₄tpy)₂][(ClO₄)₂] (1, M=Ag; 2, M=Au; dpmp=PPh₂PPhPPh₂) as precursors, six PtM₂Ln₂ heteropentanuclear adducts {[PtM₂(dpmp)₂- (C≡CC₆H₄tpy)₂][Ln(hfac)₃]₂}[(ClO₄)₂] (Ln=Nd, Er, Yb) were synthesized by the reactions of PtM₂ complexes with two equiv.Ln(hfac)₃(H₂O)₂.The crystal structures of PtAg₂Nd₂ (1Nd) and PtAu₂Nd₂ (2Nd) complexes were characterized by X-ray crystallography.PtM₂ complexes 1 and 2 exhibit intense low-energy absorption and strong room-temperature phosphorescence, which qualifies them as favorable energy donors to facilitate PtM₂→Ln energy transfer in corresponding PtM₂Ln₂ heteropentanuclear adducts.The addition of Ln(hfac)₃(H₂O)₂ to dichloromethane solution of PtM₂ complexes results in a gradually deepening of the color from yellow-green to yellow, which is associated with the enhanced and red-shifted LLCT (ligand-to-ligand charge transfer) absorption bands upon formation of the PtM₂Ln₂ arrays, as indicated by the change of the UV-vis absorption spectra of 2 upon titration with Yb(hfac)₃(H₂O)₂.Upon visible lightexcitation at 390 nm≤λ_ex≤450 nm which is the absorption region of PtM₂ chromophores, while the phosphorescence of PtM₂ chromophores vanishes mostly, near-infrared (NIR) luminescence from Nd^III, Er^III, or Yb^IIIcentersis successfully achieved through effective sensitization from PtM₂ chromophores following PtM₂→Ln energy transfer.Titration of 2 with Yb(hfac)₃(H₂O)₂ in dichloromethane induces rapid attenuation of the emission of PtM₂ chromophore so that the phosphorescence in visible region is mostly quenched whereas the NIR emission from Yb^III is remarkably enhanced upon the addition of 2 equiv.Yb(hfac)₃(H₂O)₂, further demonstrating that energy transfer from PtM₂ sensitizers to Ln^III centers indeed occurs.The rates (k_ET) of energy transfer were estimated as 6.5×10⁸ s^-1 for 1Nd, 4.42×10⁸ s^-1 for 1Er, 2.83×10⁸ s^-1 for 1Yb, 4.04×10⁸ s^-1 for 2Nd, 1.36×10⁸ s^-1 for 2Er and 5.44×10⁷ s^-1 for 2Yb species.The rates of PtM₂→Ln energy transfer following PtM₂Nd₂ > PtM₂Er₂ > PtM₂Yb₂ can be rationally elucidated by spectroscopic overlapping degree between the emission spectra of PtM₂ complexes and the f-f absorption bands of Ln^III ions.

Key words: alkyne, energy transfer, gold, NIR luminescence, platinum, rare earth, silver

Cite this article

Xu Guangtao, Li Jia, Chen Zhongning. Sensitization of NIR Lanthanide Luminescence by Heteronuclear Platinum-Silver (Gold) Complexes with Ethynyl-Functionalized 2,2’：6’,2"-Terpyridine[J]. Acta Chimica Sinica, 2014, 72(6): 667-672.

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乙炔功能化2,2’：6’,2"-三联吡啶异三核铂-银(金)配合物敏化稀土近红外发光

Sensitization of NIR Lanthanide Luminescence by Heteronuclear Platinum-Silver (Gold) Complexes with Ethynyl-Functionalized 2,2’：6’,2"-Terpyridine

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