Two-photon luminescence from polar bis-terpyridyl-stilbene derivatives of Ir(III) and Ru(II).
Two-photon luminescence from polar bis-terpyridyl-stilbene derivatives of Ir(III) and Ru(II).
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DOI：
10.1039/c0dt00750a
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发表时间：
2010-11
影响因子：
4
通讯作者：
L. Natrajan;Anita Toulmin;A. Chew;S. Magennis
中科院分区：
文献类型：
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作者：
L. Natrajan;Anita Toulmin;A. Chew;S. Magennis
合成了四种结构相关的铱（Ⅲ）和钌（Ⅱ）配合物，它们分别带有两个极性三联吡啶基-二苯乙烯衍生的发色团4-（4-{2-[4-（甲氧基）苯基]乙烯基}苯基）-2，2 ′-6 ′，2 ″-三联吡啶（三联苯甲醚）和4-（4-{2-[苯基]乙烯基}苯基）-2，2 ′-6 ′，2 ″-三联吡啶（三联二苯乙烯），并在固态和溶液中进行了表征。在固态下，Ir（III）配合物[Ir（tppyeneanisole）（2）]·3 PF（6）中吡啶基和甲苯基对向的二面角为27.1°，比Ru（II）衍生物[Ru（tppystilbene）（2）]·2 PF（6）中的二面角（35.5°）更尖锐，表明在前者化合物中存在更大程度的三联吡啶单元的π-离域。在共振和非共振激发下，研究了它们在流体溶液中的发光性质。结果表明，在近红外波段（740 ~ 820 nm）激发时，配合物均发生双光子激发，双光子吸收截面在11-67 × 10（-50）cm（4）s光子（-1）范围内。Ir（III）络合物的较大横截面反映了在固态中观察到的差异。因此，这项工作表明，这样的配合物是有前途的3D成像的发光标记物，并说明，简单的功能化的发色团和金属的选择可以导致显着的增强的双光子截面（σ（2））相比，那些更简单的杂配聚吡啶基衍生物。
Four structurally related iridium(III) and ruthenium(II) complexes bearing two polar terpyridyl-stilbene derived chromophores 4-(4-{2-[4-(methoxy)phenyl]ethenyl}phenyl)-2,2'-6',2''-terpyridine (ttpyeneanisole) and 4-(4-{2-[phenyl]ethenyl}phenyl)-2,2'-6',2''-terpyridine (tpystilbene) have been synthesised and characterised in the solid state and in solution. In the solid state, the dihedral angle subtending the pyridyl and tolyl groups of 27.1° in the Ir(III) complex [Ir(ttpyeneanisole)(2)]·3PF(6) is more acute than in the Ru(II) derivative [Ru(tpystilbene)(2)]·2PF(6) (35.5°), indicating the presence of a greater degree of π-delocalisation across the terpyridine unit in the former compound. Their luminescence properties in fluid solution have been investigated following both resonant and non-resonant excitation. We have shown that each of the complexes undergoes two-photon excitation when excited in the near infrared (740 to 820 nm), with two-photon absorption cross sections in the range 11-67 × 10(-50) cm(4) s photon(-1). The larger cross sections for the Ir(III) complexes reflect the differences observed in the solid state. This work therefore demonstrates that such complexes are promising as luminescent markers for 3D imaging and illustrates that simple functionalisation of the chromophores and the choice of metal can lead to marked enhancements in the two-photon cross sections (σ(2)) compared to those of simpler heteroleptic polypyridyl based derivatives.