Jean-Claude Bunzli - NIR lanthanide luminescence by energy transfer from appended terpyridine-boradiazaindacene dyes

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  Publication Details (including relevant citation   information):

  Ziessel,R.F., Ulrich,G., Charbonniere,L., Imbert,D.,   Scopelliti,R., Bunzli,J.C.G. Chemistry-A European   Journal 2006 12 (19) 5060-5067

  Abstract: Mononuclear trivalent lanthanide   complexes with formula [Ln(L)(NO3)(3)] [in which   L=4,4-difluoro-8-(2':2";6":2"'-terpyridin-4"-yl)-   1,3,5,7-tetramethyl-2,6-diethyl-4-bora3a,4a-diaza-s-indacene   (Boditerpy)] are reported for Ln = Yb, Nd, Er, La and Gd.   According to the crystal structure of the Yb complex, the   lanthanide ion is bound to the terdentate terpyridine and the   inner coordination sphere of the nine-coordinate lanthanide ion   is completed by three bidentate nitrate anions. The coordination   polyhedron can be described as a distorted tricapped antiprism.   The terpyridine chelate is almost planar and tilted by nearly 60   degrees from the indacene subunit. FT-IR spectra confirm the   bidentate binding mode of the nitrate anions for the other   complexes. NMR and ES-MS spectra (through characteristic isotopic   patterns) confirm the chemical formu- lation. The complexes have   high molar absorption coefficients in the visible spectral region   (65000M(-1)cm(-1) at 529 nm) and display sizeable NIR   luminescence (900 to 1600 nm, for Ln = Yb, Nd and Er), upon   irradiation through the electronic state of the indacene moiety   at 514 nm. Crystal-field splitting was analysed at low   temperature. The quantum yield of the Yb solution (10(-4)M) in   dichloromethane amounts to 0.31%, corresponding to a   sensitisation efficacy of the ligand of ca.63 %

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