Zhong Qi, Wang Huaishan, Qian Guodong, Wang Zhiyu, Zhang Jiahua, Qiu Jianrong, Wang Minquan
Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China.
Inorg Chem. 2006 May 29;45(11):4537-43. doi: 10.1021/ic051697y.
Three beta-diketonate complexes of erbium and ytterbium, Er(HFA)3(TPPO)3, Yb(HFA)3(TPPO)3, and Er(1/2)Yb(1/)(2)(HFA)3(TPPO)2 (HFA = hexafluoroacetylacetonate, TPPO = triphenylphosphine oxide) are synthesized and structurally characterized, and their luminescent properties are examined in detail. Compared with monometallic complexes Er(HFA)3(TPPO)3 and Er(HFA)3(TPPO)3, the stoichiometrically Er-Yb cocrystalline complex Er(1/2)Yb(1/2)(HFA)3(TPPO)2 exhibits special indirect near-infrared (NIR) luminescence with the acceptor and sensitizer (donor) coexisting in a single crystal. Of interest is that the NIR luminescence of the erbium ion in Er(1/2)Yb(1/2)(HFA)3(TPPO)2 is significantly enhanced because of the coexistence of the ytterbium ion through the energy-transfer between the ytterbium and erbium ions. The estimated donor-acceptor energy-transfer critical radii R(C,DA), obtained from the Förster model, are in good agreement with those determined from the single X-ray crystal structure, confirming the dipole-dipole character for such a Yb-Er energy-transfer process.
合成并对铒和镱的三种β-二酮配合物Er(HFA)3(TPPO)3、Yb(HFA)3(TPPO)3以及Er(1/2)Yb(1/2)(HFA)3(TPPO)2(HFA = 六氟乙酰丙酮,TPPO = 三苯基氧化膦)进行了结构表征,并详细研究了它们的发光性质。与单金属配合物Er(HFA)3(TPPO)3和Yb(HFA)3(TPPO)3相比,化学计量比的Er-Yb共晶配合物Er(1/2)Yb(1/2)(HFA)3(TPPO)2在单晶中同时存在受体和敏化剂(供体)的情况下表现出特殊的间接近红外(NIR)发光。有趣的是,由于镱离子的共存,通过镱离子和铒离子之间的能量转移,Er(1/2)Yb(1/2)(HFA)3(TPPO)2中铒离子的近红外发光显著增强。从Förster模型获得的估计供体-受体能量转移临界半径R(C,DA)与从单X射线晶体结构确定的半径吻合良好,证实了这种Yb-Er能量转移过程具有偶极-偶极特性。