Highly emitting near-infrared lanthanide "encapsulated sandwich" metallacrown complexes with excitation shifted toward lower energy.
Highly emitting near-infrared lanthanide "encapsulated sandwich" metallacrown complexes with excitation shifted toward lower energy.
复制标题
高度发射的近红外灯笼“封装的三明治”金属配合物，激励朝着较低的能量转移。
DOI：
10.1021/ja4113337
复制
发表时间：
2014-01-29
影响因子：
15
通讯作者：
Pecoraro VL
中科院分区：
文献类型：
--
作者：
Trivedi ER;Eliseeva SV;Jankolovits J;Olmstead MM;Petoud S;Pecoraro VL
近红外（NIR）发光镧系元素配合物在实际应用中具有很大的前景，因为它们的光学性质与有机荧光团和半导体纳米颗粒相比具有几个互补的优势。镧系发光的基本挑战是通过合适的发色团敏化。金属冠醚（MC）基序的使用是一种创新的策略，安排在一个良好的控制距离的镧系元素阳离子的几个有机敏化剂。本文报道了一系列镧系元素的“包封夹心”MC配合物，其形式为Ln 3 +[12-MCZn（II），quinHA-4]2[24-MCZn（II），quinHA-8]（Ln 3 +[Zn（II）MCquinHA]），其中MC骨架由Zn 2+离子和基于喹哪啶二异羟肟酸（quinHA）的四齿发色配体自组装而成。第一代的发光MC先前提出，但由于在UV中的激发波长而受到限制。我们在这里报告说，通过MC组装体发色团的设计，我们已经将吸收波长显着向较低能量（450 nm）移动。除了这种近可见的配体间和/或配体内电荷转移吸收之外，Ln 3 +[Zn（II）MCquinHA]还表现出非常高的量子产率、长的发光寿命（CD 3 OD; Yb 3+，QLnL = 2.88（2）%，τobs = 150.7（2）μs; Nd 3+，QLnL = 1.35（1）%，τobs = 4.11（3）μs; Er 3+，QLnL = 3.60（6）·10- 2%，τobs = 11.40（3）μs），具有良好的光稳定性。Nd 3+和Er 3 + MCs在固态和氘代溶剂中的量子产率，在低能量激发时，是含有C-H键的近红外发射镧系元素络合物中的最高值。MC策略的多功能性允许通过配体敏化剂的适当设计来修改激发波长和吸收率，从而提供具有可调性质的高效平台。
Near-infrared (NIR) luminescent lanthanide complexes hold great promise for practical applications, as their optical properties have several complementary advantages over organic fluorophores and semiconductor nanoparticles. The fundamental challenge for lanthanide luminescence is their sensitization through suitable chromophores. The use of the metallacrown (MC) motif is an innovative strategy to arrange several organic sensitizers at a well-controlled distance from a lanthanide cation. Herein we report a series of lanthanide “encapsulated sandwich” MC complexes of the form Ln3+[12-MCZn(II),quinHA-4]2[24-MCZn(II),quinHA-8] (Ln3+[Zn(II)MCquinHA]) in which the MC framework is formed by the self-assembly of Zn2+ ions and tetradentate chromophoric ligands based on quinaldichydroxamic acid (quinHA). A first-generation of luminescent MCs was presented previously but was limited due to excitation wavelengths in the UV. We report here that through the design of the chromophore of the MC assembly, we have significantly shifted the absorption wavelength toward lower energy (450 nm). In addition to this near-visible inter- and/or intraligand charge transfer absorption, Ln3+[Zn(II)MCquinHA] exhibits remarkably high quantum yields, long luminescence lifetimes (CD3OD; Yb3+, QLnL = 2.88(2)%, τobs = 150.7(2) μs; Nd3+, QLnL = 1.35(1)%, τobs = 4.11(3) μs; Er3+, QLnL = 3.60(6)·10–2%, τobs = 11.40(3) μs), and excellent photostability. Quantum yields of Nd3+ and Er3+ MCs in the solid state and in deuterated solvents, upon excitation at low energy, are the highest values among NIR-emitting lanthanide complexes containing C–H bonds. The versatility of the MC strategy allows modifications in the excitation wavelength and absorptivity through the appropriate design of the ligand sensitizer, providing a highly efficient platform with tunable properties.
登录
查看更多内容
影响因子：
4.9
作者：
Abdelhameed, Reda M.;Carlos, Luis D.;Rocha, Joao
通讯作者：
Rocha, Joao
影响因子：
5.5
作者：
Andolina CM;Klemm PJ;Floyd WC 3rd;Fréchet JM;Raymond KN
通讯作者：
Raymond KN
影响因子：
20.6
作者：
Buenzli, Jean-Claude G.;Chauvin, Anne-Sophie;Eliseeva, Svetlana V.
通讯作者：
Eliseeva, Svetlana V.
DOI：
10.1016/s0168-1273(07)37035-9
发表时间：
2007-01-01
期刊：
HANDBOOK ON THE PHYSICS AND CHEMISTRY OF RARE EARTHS, VOL 37: OPTICAL SPECTROSCOPY
影响因子：
--
作者：
Comby, Steve;Buenzli, Jean-Claude G.
通讯作者：
Buenzli, Jean-Claude G.
影响因子：
17.1
作者：
Comby, Steve;Gunnlaugsson, Thorfinnur
通讯作者：
Gunnlaugsson, Thorfinnur