Jean-Claude Bunzli - Highly Luminescent and Triboluminescent Coordination Polymers Assembled from Lanthanide beta-Diketonates and Aromatic Bidentate O-Donor Ligands

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      Eliseeva,S.V., Pleshkov,D.N., Lyssenko,K.A., Lepnev,L.S.,   Bunzli,J.C.G., Kuzminat,N.P. Inorganic Chemistry  2010 49 (20) 9300-9311

      Abstract: The reaction of hydrated lanthanide   hexafluoroacetylacetonates, [Ln(hfa)(3)(H(2)O)(2)], with   1,4-disubstituted benzenes afforded a new series of   one-dimensional coordination polymers [Ln(hfa)(3)(Q)](infinity),   where Ln = Eu, Gd, Tb, and Lu and Q = 1,4-diacetylbenzene (acbz),   1,4-diacetoxybenzene (acetbz), or 1,4-dimethyltherephtalate   (dmtph). X-ray single crystal analyses reveal   [Ln(hfa)(3)(acbz)](infinity) (Ln = Eu, Gd, Tb) consisting of   zigzag polymeric chains with Ln Ln Ln angles equal to 128   degrees, while the arrays are more linear in   [Eu(hfa)(3)(acetbz)infinity and [Eu(hfa)(3)(dmtph)](infinity),   with Ln Ln Ln angles of 165 degrees and 180 degrees,   respectively. In all structures, Ln(III) ions are 8-coordinate   and lie in distorted square-antiprismatic environments. The   coordination polymers are thermally stable up to 180-210 degrees   C under a nitrogen atmosphere. Their volatility has been tested   in vacuum sublimation experiments at 200-250 degrees C and 10(-2)   Torr: the metal organic frameworks with acetbz and dmtph can be   quantitatively sublimed, while [Ln(hfa)(3)(acbz)](infinity)   undergoes thermal decomposition. The triplet state energies of   the ancillary ligands, 21 600 (acetbz), 22 840 (acbz), and 24 500   (dmtph) cm(-1), lie in an ideal range for sensitizing the   luminescence of Eu(III) and/or Tb(III). As a result, all of the   [Ln(hfa)(3)(Q)](infinity) polymers display bright red or green   luminescence due to the characteristic (5)D(0)->(7)F(J)(J=0-4)   or (5)D(4) -> (7)F(J) (J=6-0) transitions, respectively.   Absolute quantum yields reach 51(Eu) and 56(Tb) % for the   frameworks built from dmtph. Thin films of   [Eu(hfa)(3)(Q)](infinity) with 100-170 nm thickness can be   obtained by thermal evaporation (P<3 x 10(-5) Torr, 200-250   degrees C). They are stable over a long period of time, and their   photophysical parameters are similar to those of the bulk samples   so that their use as active materials in luminescent devices can   be envisaged. Mixtures of [Ln(hfa)(3)(dmpth)](infinity) with Ln =   Eu and Tb yield color-tunable microcrystalline materials from red   to green. Finally, the crystalline samples exhibit strong   triboluminescence, which could be useful in the design of   pressure and/or damage detection probes

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