Highly luminescent and triboluminescent coordination polymers assembled from lanthanide β-diketonates and aromatic bidentate O-donor ligands

摘要

The reaction of hydrated lanthanide hexafluoroacetylacetonates, [Ln(hfa)_3(H_2O)_2], with 1,4-disubstituted benzenes afforded a new series of one-dimensional coordination polymers [Ln(hfa)_3(Q)]_∞, 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)]_∞, (Ln = Eu, Gd, Tb) consisting of zigzag polymeric chains with Ln-Ln-Ln angles equal to 128°, while the arrays are more linear in [Eu(hfa)_3(acetbz)]_∞ and [Eu(hfa)_3(dmtph)]_∞, with Ln-Ln-Ln angles of 165° and 180°, 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 °C under a nitrogen atmosphere. Their volatility has been tested in vacuum sublimation experiments at 200-250 °C and 10~(-2) Torr: the metal-organic frameworks with acetbz and dmtph can be quantitatively sublimed, while [Ln(hfa) _3(acbz)]_∞ 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)]_∞, polymers display bright red or green luminescence due to the characteristic ~5D_0 ∞ ~7F_J (J=0-4) or ~5D_4 → ~7F_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)]_∞, with 100-170 nm thickness can be obtained by thermal evaporation (P<3 × 10~(-5) Torr, 200-250 °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)]_∞ 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.