Isotope effect of crystal water on emission lifetime of Ru(dbb)2(CN)2･2H2O (dbb = 4,4'-di-tert-butyl-2,2'-bipyridine) crystal
Isotope effect of crystal water on emission lifetime of Ru(dbb)2(CN)2･2H2O (dbb = 4,4'-di-tert-butyl-2,2'-bipyridine) crystal
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结晶水对Ru(dbb)2(CN)2･2H2O (dbb = 4,4-二叔丁基-2,2-联吡啶)晶体发射寿命的影响
DOI：
10.1039/c3ra23362f
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发表时间：
2013
期刊：
影响因子：
3.9
通讯作者：
T. Suzuki
中科院分区：
文献类型：
--
作者：
K. Shinozaki;K. Tenmyoa;T. Suzuki
我们研究了结晶水对固态Ru(dbb)2(CN)2·2H2O发射寿命的同位素效应。 Ru(dbb)2(CN)2·2D2O (dbb = 4,4′-二叔丁基-2,2′-联吡啶)和Ru(dbb)2(CN)2·2H2O在298 K下的发射寿命比为τD/τH = 1.14 ± 0.05。从晶体结构分析得出，结晶水和5,5′-之间存在氢键作用。 dbb 配体的 3,3'-H 原子和/或 3,3'-H 原子比水和 CN 配体之间的同位素效应更有效地促进结晶水对发射寿命的影响。随着温度升高，两个水分子在 310-345 K 和超过 385 K 的温度下逐步从由 dbb 部分构建的疏水通道中释放出来。将非水合晶体 Ru(dbb)2(CN)2 在 298 K 下暴露于 H2O 或 D2O 蒸气中，分别得到 Ru(dbb)2(CN)2·2H2O 或 Ru(dbb)2(CN)2·2D2O。在H2O-D2O混合气氛下，结晶水中H2O和D2O的比例与混合气氛中H2O和D2O的统计分布之间不存在相关性。即使在 70% D2O 气氛下，也观察到 Ru(dbb)2(CN)2 晶体中 H2O 的选择性吸附。
We studied the isotope effect of crystal water on the emission lifetime of Ru(dbb)2(CN)2·2H2O in the solid state. The emission lifetime ratio of Ru(dbb)2(CN)2·2D2O (dbb = 4,4′-di-tert-butyl-2,2′-bipyridine) and Ru(dbb)2(CN)2·2H2O was determined to be τD/τH = 1.14 ± 0.05 at 298 K. From a crystal structural analysis, it was concluded that hydrogen bonding between crystal water and the 5,5′- and/or 3,3′-H atoms of the dbb ligands contributed more effectively to the isotope effect of crystal water on emission lifetime than that between water and the CN ligands. With increasing temperature, two water molecules were released at 310–345 K and over 385 K stepwise from hydrophobic channels constructed from dbb moieties. Exposure of the non-hydrated crystal, Ru(dbb)2(CN)2, to H2O or D2O vapor at 298 K gave Ru(dbb)2(CN)2·2H2O or Ru(dbb)2(CN)2·2D2O, respectively. Under a H2O–D2O mixed atmosphere, there was no correlation between the ratio of H2O and D2O in crystal water and the statistical distribution of H2O and D2O in the mixed atmosphere. Even under a 70% D2O atmosphere, selective sorption of H2O in the crystal of Ru(dbb)2(CN)2 was observed.