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New Lamellar Silver Thiolate Coordination Polymers with Tunable Photoluminescence Energies by Metal Substitution
摘要： The structures of two lamellar silver thiolate coordination polymers [Ag(p-SPhCO2H)]n (1) and [Ag(p-SPhCO2Me)]n (2) are described for the first time. Their inorganic part is composed of distorted Ag3S3 honeycomb networks separated by noninterpenetrated thiolate ligands. The main difference between the two compounds arises from dimeric hydrogen bonds present for the carboxylic acids. Indepth photophysical studies show that the silver thiolates implying luminescence exhibit multiemission properties, the synthesis of a thermochromism. More interestingly, the synthesis of a heterometallic lamellar compound, [Ag0.85Cu0.15(p-SPhCO2H)]n (3), allows to obtain mixed metal thiolate coordination polymers and to tune the photophysical properties with the excitation wavelengths from a green vibronic luminescence to a single red emission band.
关键词： lamellar silver thiolate,photoluminescence,thermochromism,metal substitution,coordination polymers
更新于2025-09-04 15:30:14
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Wide-Range UV-to-Visible Excitation of Near-Infrared Emission and Slow Magnetic Relaxation in Ln <sup>III</sup> (4,4′-Azopyridine-1,1′-dioxide)[Co <sup>III</sup> (CN) <sub/>6</sub> ] <sup>3–</sup> Layered Frameworks
摘要： Trivalent lanthanide ions combined with two linkers, organic 4,4′-azopyridine-1,1′-dioxide (apdo), and inorganic hexacyanidocobaltate(III), gave a series of magnetoluminescent coordination polymers, [{LnIII(apdo)(H2O)4}{CoIII(CN)6}]·2H2O (Ln = Nd, 1; Tb, 2; Dy, 3; Er, 4; Tm, 5; Yb, 6). They are hybrid organic?inorganic layered frameworks composed of cyanido-bridged {Ln2(μ-NC)4Co2} squares linked by Ln?apdo?Ln bridges into a coordination network of a mixed 4- and 8-metal ring topology. Lanthanide(III) complexes, [LnIII(μ-apdo)2(H2O)4(μ-NC)2]+, of a distorted dodecahedral geometry are isolated by diamagnetic [CoIII(CN)6]3? and apdo linkers. As a result, 1?6 reveal field-induced slow relaxation of magnetization, with typical temperature-dependent relaxation of a single-ion origin for NdIII-containing 1, DyIII-containing 3, and YbIII-containing 6. The related alternate-current magnetic data were precisely analyzed, indicating the multiple magnetic relaxation pathways, including a direct process, strong quantum tunneling of magnetization, non-negligible Raman processes, and crucial two-phonon Orbach thermal relaxation. The thermal energy barriers of the Orbach process, ΔE/kB, are 15.1(9) K with τ0 = 9.8(9) × 10?6 s at Hdc = 4500 Oe, 16.1(8) K with τ0 = 9.0(9) × 10?5 s at Hdc = 1500 Oe, and 17.3(6) K with τ0 = 3.2(7) × 10?6 s at Hdc = 700 Oe, for 1, 3, and 6, respectively, proving the single-molecule magnet (SMM) behavior. Because of the presence of [Co(CN)6]3?, 1?6 show strong UV absorption, while the chromophoric apdo leads to the strong absorption in the visible range. As a result, the visible 4f/3d metal-centered emission is quenched, but the near-infrared luminescence from NdIII and YbIII is observed in 1 and 6, respectively. It is realized by Co-to-Ln metal-to-metal, and apdo-to-Ln ligand-to-metal energy transfers; thus, broad UV-to-visible excitation can be explored. Compounds 1?6 form a novel family of functional bimetallic assemblies, incorporating NIR-emissive SMMs as presented for NdCo (1) and YbCo (6) derivatives.
关键词： single-molecule magnets,near-infrared luminescence,coordination polymers,magnetoluminescent,lanthanide
更新于2025-09-04 15:30:14
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Rare earth phosphors based on spherical infinite coordination polymers
摘要： A novel luminescent infinite coordination polymer (Tb-M), constructed by the interaction between Tb3+ ions and 3,5-pyrazoledicarboxylate and malonate linkers, was prepared by water microwave-assisted synthesis. The material self-assembles into amorphous microspherical particles. Under UV excitation, a very intense green luminescence is observed by the naked eye at room temperature for Tb-M. A Gd3+ analogue compound (Gd-M) was also synthesized. Successful attempts at codoping Tb-M and Gd-M samples with Eu3+ and Dy3+ ions were carried out and different emission colors were obtained, including white-light emission.
关键词： infinite coordination polymers,rare earth phosphors,microwave-assisted synthesis,luminescence,white-light emission
更新于2025-09-04 15:30:14
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Lanthanide-Based Coordination Polymers With 1,4-Carboxyphenylboronic Ligand: Multiemissive Compounds for Multisensitive Luminescent Thermometric Probes
摘要： Reactions in water of lanthanide chlorides with the sodium salt of 1,4-carboxyphenylboronic acid lead to two series of isostructural compounds with respective general chemical formulas [Ln(cpb)3(H2O)2]∞ for Ln = La or Ce and ·(cpb)]∞ for Ln = Pr?Lu (except Pm) plus Y. Hetero-lanthanide coordination polymers that are isostructural to the second series have been synthesized, and their photophysical properties have been studied. This study evidences that it is possible to design multiemissive lanthanide-based coordination polymers that could ?nd their application as multigauge luminescent thermometric probes.
关键词： 1,4-carboxyphenylboronic acid,lanthanide,luminescent thermometric probes,coordination polymers
更新于2025-09-04 15:30:14
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Structural and Luminescence Properties of Anthracene- and Biphenyl-Based Lanthanide Bisphosphonate Ester Coordination Polymers
摘要： Coordinative networks containing lanthanide ions attached via phosphonate ester functionalities provide remarkable luminescence properties. On the basis of ditopic phosphonic ester ligands with biphenylene and 9,10-anthracenylene bridges, a series of compounds with formal composition {[M(NO3)3]L}n or {[M(NO3)3]2(L1)3}n (L = C28H40O6P2; L1 = C26H40O6P2) with M = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y have been synthesized, structurally characterized, and the luminescence behavior was explored in the visible and NIR spectral regions, where applicable. In contrast to closely related networks based on biphenyl bisphosphonate esters from previous work, no evidence for ligand-to-metal energy transfer could be observed, despite strong near-infrared emission in some cases. Unique behavior is found for the Eu derivative with the 9,10-anthracenylene bridge, which is nonemissive, showing neither ligand- nor metal-based emission.
关键词： lanthanide,phosphonate ester,luminescence,NIR emission,coordination polymers
更新于2025-09-04 15:30:14