TY - JOUR
T1 - 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
AU - Shinozaki, Kazuteru
AU - Tenmyo, Kazuhiro
AU - Suzuki, Takayoshi
N1 - Copyright:
Copyright 2013 Elsevier B.V., All rights reserved.
PY - 2013/5/28
Y1 - 2013/5/28
N2 - 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-D 2O 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.
AB - 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-D 2O 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.
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U2 - 10.1039/c3ra23362f
DO - 10.1039/c3ra23362f
M3 - Article
AN - SCOPUS:84877286035
SN - 2046-2069
VL - 3
SP - 7579
EP - 7584
JO - RSC Advances
JF - RSC Advances
IS - 20
ER -