Phosphorescent organogels via "metallophilic" interactions for reversible RGB-color switching
Phosphorescent organogels via "metallophilic" interactions for reversible RGB-color switching
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DOI：
10.1021/ja0441007
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发表时间：
2005-01-12
影响因子：
15
通讯作者：
Aida, T
中科院分区：
文献类型：
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作者：
Kishimura, A;Yamashita, T;Aida, T
在己烷中含有长烷基链(1)的三核金(l)吡唑酸盐配合物通过Au(l)-Au(I)亲金属相互作用自组装，形成发光红色的有机凝胶(λ (em) = 640 nm, λ (ext) = 284 nm)。扫描电子显微镜（SEM）和x射线衍射（XRD）分析显示，含有1的风干凝胶存在严重纠缠的纤维，每个纤维由1的矩形填充柱状组合组成。用少量Ag+掺杂有机凝胶，在不破坏凝胶的情况下产生蓝色发光(lambda(em) = 458 rim, lambda(ext) = 370 nm)，而用十六烷基三甲基氯化铵去除掺杂Ag+，可以完全恢复原始的红色发光凝胶。加热后，由于亲金相互作用的不稳定，这些有机凝胶经历凝胶到溶胶的转变，其中未掺杂体系的红色发光变得几乎不可见，而Ag+掺杂体系的蓝色发光变为绿色(lambda（em) = 501 nm, lambda(ext) = 370 nm）。冷却时，这些溶液发生凝胶化并同步恢复原始发光。观察到的RGB（红-绿-蓝）发光都是长寿命的（3-6 μ m），并且分配给三态激发态的电子跃迁。
A trinuclear Au(l) pyrazolate complex bearing long alkyl chains (1) in hexane self-assembles via a Au(l)-Au(I) metallophilic interaction, to form a red-luminescent organogel (lambda(em) = 640 nm, lambda(ext) = 284 nm). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis of an air-dried gel with 1 show the presence of heavily entangled fibers, each consisting of a rectangularly packed columnar assembly of 1. Doping of the organogel with a small amount of Ag+ results in a blue luminescence (lambda(em) = 458 rim, lambda(ext) = 370 nm) without disruption of the gel, while removal of doped Ag+ with cetyltrimethylammonium chloride results in complete recovery of the original red-luminescent gel. Upon heating, these organogels undergo gel-to-sol transition due to the destabilization of the metallophilic interactions, where the red luminescence of the nondoped system becomes hardly visible, while the blue luminescence of the Ag+-doped system turns green (lambda(em) = 501 nm, lambda(ext) = 370 nm). On cooling, these solutions undergo gelation and synchronously recover the original luminescences. The observed RGB (red-green-blue) luminescences are all long-lived (3-6 mus) and assigned to electronic transitions from triplet-excited states.