Alkyl chain elongation and acyl group effects in a series of Eu/Tb complexes with hexadentate π-electronic skeletons and their enhanced luminescence in solutions

Dalton Transactions : an International Journal of Inorganic Chemistry
Shuhei OgataMiki Hasegawa

Abstract

Five Eu complexes with long alkyl chain groups, abbreviated as EuLCx ("x" indicates the number of methylene groups: x = 8, 12, 14, 18, and 22), were synthesized to evaluate their structural and luminescence properties in chloroform. The mother helicate Eu complex, EuL, which has two bipyridine moieties bridged by an ethylenediamine, has been previously reported. A reduced form in which the azomethine groups of L also coordinated to the Eu ion, EuLH, was newly prepared. EuLH also adopts a helicate molecular structure based on single crystal X-ray structural analysis. The amine hydrogens of the bridging ethylenediamine of LH are active sites for substitution and were exchanged with five different alkyl chains to form EuLCx. Luminescence band positions and shapes of EuLCx in chloroform were completely identical, with a quantum yield of 37.1 ± 1.2 and a lifetime of around 1.25 ms. This indicates that the environments surrounding the Eu ion in the various complexes are all similar. Luminescence quantum yields of TbLH and TbLC18 are also strengthened, 48.7% in acetonitrile and 55% in chloroform, respectively. Potential energy surfaces were also described by using density functional theory, suggesting the possibility of a 1 : 2 comple...Continue Reading

References

Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Dec 22, 2009·Chemical Society Reviews·Svetlana V Eliseeva, Jean-Claude G Bünzli
Dec 15, 2010·Chemical Society Reviews·Hana Robson MarsdenAlexander Kros
Jul 30, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Hang XuBin Zhao
Dec 5, 2017·Physical Chemistry Chemical Physics : PCCP·Miho HatanakaMiki Hasegawa

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Methods Mentioned

BETA
X-ray
phosphorescence
column chromatography

Software Mentioned

97
Gaussian09
Bruker APEX - II
SHELX

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