Rare-Earth-Incorporated Tellurotungstate Hybrids Functionalized by 2-Picolinic Acid Ligands: Syntheses, Structures,...

A series of organic-inorganic rare-earth-incorporated tellurotungstate hybrids, Na₄[RE₂(H₂O)₄(pica)₂W₂O₅][(RE(H₂O)W₂(Hpica)₂O₄)(B-β-TeW₈O₃₀H₂)₂]₂·38H₂O (RE = La^III (1), Ce^III (2), Nd^III (3), Sm^III (4), Eu^III (5); Hpica = 2-picolinic acid), were prepared via a one-step assembly reaction of Na₂WO₄·2H₂O, RE(NO₃)₃·6H₂O, K₂TeO₃, Hpica, and triethylamine (tea). Notably, the solubilization of tea toward Hpica and the solubilization of Hpica toward RE cations in the reaction system play an important role in the formation of 1-5. The most significant feature of 1-5 consists of an intriguing tetrameric [RE₂(H₂O)₄(pica)₂W₂O₅][(RE(H₂O)W₂(Hpica)₂O₄)(B-β-TeW₈O₃₀H₂)₂]₂^4- polyoxoanion constructed from two tetravacant Keggin sandwich-type [(RE(H₂O)W₂(Hpica)₂O₄)(B-β-TeW₈O₃₀H₂)₂]^5- entities linked by a RE-W-Hpica {RE₂(H₂O)₄(pica)₂W₂O₅}⁶⁺ cluster, in which Hpica ligands not only play a key bridging role in linking RE and W centers by carboxylic groups in an irregular N-O-RE-O-W-O six-membered-ring motif but also can directly chelate with W centers via N and O atoms in a stable N-O-C-O-W five-membered-ring fashion. 1-5 represent rare organic-inorganic hybrid RE-substituted tellurotungstates. Moreover, the solid-state photoluminescence properties of 3-5 have been deeply investigated, and these compounds exhibit the characteristic emission stemming from intra-4f transitions of RE ions. The energy transfer of the O → W transitions sensitizing the emission of Sm^III centers in 4 is convincingly proved by time-resolved emission spectra (TRES); the increase in the strongest typical emission of Sm^III ions at a decay time of 17 μs is accompanied by the decline of O → W emission, and the CIE 1931 diagram was obtained from the corresponding TRES. Furthermore, a comparison of the luminescence behaviors of 5 in the solid state and in solution reveals the structural skeletal integrity of 5 in solution and a shorter decay lifetime in the solution caused by the high-frequency O-H oscillators.