Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Enhanced Emission of Nd3+ in Liquid Systems: Formation of Symmetrical Rigid Shells of Tightly Solvated DMSO Molecules and Weakly Coordinated Low-Vibrational β-Diketonato Ligands
Yasuchika HasegawaMitsunori IwamuroKei MurakoshiYuji WadaRyuichi ArakawaTatsuhiko YamanakaNobuaki NakashimaShozo Yanagida
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1998 Volume 71 Issue 11 Pages 2573-2581


Coordination structures of neodymium(III) complexes with some β-diketones were investigated in terms of their correlations with emission efficiency in deuterated dimethylsulfoxide (DMSO-d6). The analysis of UV-vis spectra, 13C NMR, electrospray mass spectrometry (ES-MS) spectra, XANES and EXAFS analysis of tris(hexafluoroacetylacetonato)neodymium(III) complex, [Nd(hfa-H)3(H2O)2], and tris[bis(perfluorooctanoyl)methanato]neodymium(III), [Nd(pom-H)3], in DMSO indicated that the deuterated tris(hexafluoroacetylacetonato)neodymium(III), Nd(hfa-D)3, and deuterated tris[bis(perfluorooctanoyl)methanato]neodymium(III), Nd(pom-D)3, in DMSO-d6 should have a symmetrical, rigid and bulky shell composed of six inner-coordinating DMSO molecules and three weakly coordinating hfa-D and pom-D molecules. The improvement in the emission efficiency of the neodymium complexes with the low vibrational and weakly coordinating β-diketonates in DMSO-d6 was ascribed to their symmetrical rigid coordination structures, which should suppress radiationless transition via vibrational excitation and energy migration in the fluid system.

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© 1998 The Chemical Society of Japan
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