Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric; Karram, Joseph P.; Kent, Claudia; Eugene, Vadine E.; Chan, Benny C.; Lill, Daniel T. de

doi:10.1016/j.jssc.2015.01.014

Cited by 14 publications

(5 citation statements)

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“…Compounds 1 – 9 ,− , were chosen due to their varying topologies, number of coordinated OH oscillators, and linker composition. The target structures were synthesized with Eu(III), Gd(III), and Tb(III) ions, and structures were confirmed with powder X-ray diffraction.…”

Section: Resultsmentioning

confidence: 99%

“…Another CP system was synthesized with a 1,3-benzenedicarboxylic acid (1,3-BDC), [Ln 2 (1,3-BDC) 3 (H 2 O) 2 ] ( 5 ) . A system with a highly efficient sensitizing linker with two aromatic rings bridged by an ether oxygen, 4,4′-oxybis(benzoic acid) (OBA), [Ln 2 (OBA) 3 (H 2 O) 5.5 ]·0.5H 2 O ( 6 ), as well as three CPs previously reported by our group, [Ln(BPDC) 3 (H 2 O) 3 ] ( 7 ), [Ln(PYDC)(HPYDC)(H 2 O)] ( 8 ), and [Ln(FDC)(HFDC)(H 2 O)] ( 9 ) (BPDC = 4,4′-benzophenonedicarboxylic acid, PYDC = 2,3-pyridinedicarboxylic acid, and FDC = 3,4-furandicarboxylic acid), were also chosen. The linkers for each CP studied had the energy of their singlet and triplet states determined from molecular complexes as well as the singlet and triplet bands of the CPs.…”

Section: Introductionmentioning

confidence: 99%

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A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal–Organic Framework Materials

et al. 2017

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Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal–Organic Framework Materials

et al. 2017

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“…If 3 T is of appropriate energy to resonate with an excited state manifold of the Ln, ET can occur. Once populated, radiative emission (L) from the excited Ln can then ensue if the energy is not deactivated by any number of competing NR mechanisms. − To evaluate the overall efficiency of this process, emission quantum yields are often determined. Together with excited state lifetimes and energy values of the ligand’s 1 S and 3 T, a simplified qualitative description of these processes is obtained relatively easily.…”

Section: Introductionmentioning

confidence: 99%

“…Extending these concepts to CPs has led to the development of luminescent materials that behave similarly though not identical to molecular complexes. , CPs sit at the crossroad between discrete molecular species and extended inorganic network solids; at this interface between molecule and solid, the luminescent properties are a combination of both systems and behave differently than each isolated system alone. Essentially all discussions of sensitized luminescence of CPs reference the antenna effect, effectively comparing them directly to molecular complexes. ,,− ,− ,− In doing so, there is no regard to the infinite, network arrangement of CP structures, which results in fundamentally different behavior than with molecular species.…”

Section: Introductionmentioning

confidence: 99%

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C₁₅H₉O₅)₃(H₂O)₃]_n (Ln = Eu, Tb)

et al. 2016

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A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

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“…At present, most studies on the luminescence of trivalent terbium ions are focused on Tb(III) complexes (Pereira et al, 2012;Essawy, 2014;Yue et al, 2014;Greig et al, 2015). Because of the thermal and chemical stability and the minimal toxicity, investigation of Tb 3+ -doped inorganic materials is very worthwhile.…”

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confidence: 99%

Intercalation of Tb(III) into magadiite and characterization of Tb-intercalated magadiites

et al. 2016

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The intercalation of Tb(III) into layered magadiite is achieved by three-step ion exchanges with H+/Na+, TBA+ (tetra-n-butylammonium ions)/H+ and Tb(EDTA)3+/TBA+. Various techniques, including powder X-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive X-ray (SEM-EDX), thermogravimetric and differential thermogravimetry (TG-DTG), Fourier transform infrared (FTIR) spectroscopy, and photoluminescent spectroscopy (PL), were employed to characterize the Tb-intercalated magadiites. The XRD results revealed that the basal spacing of the Tb-intercalated magadiites was obviously larger than that of the Na-magadiite, confirming the intercalation. The IR spectra showed no bands attributable to EDTA in the Tb-intercalated magadiites, indicating that the EDTA has broken away from Tb(III)-ETDA complexes during ion exchange. Moreover, the basal spacing of Tb-intercalated magadiite tends to increase slightly with the increase in water content in the Tb-intercalated magadiite. The PL spectra show weak emissions, attributed to 5D4-7FJ (J = 3, 4, 5, 6) transitions of Tb3+.

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Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

Cited by 14 publications

References 36 publications

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal–Organic Framework Materials

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal–Organic Framework Materials

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C₁₅H₉O₅)₃(H₂O)₃]_n (Ln = Eu, Tb)

Intercalation of Tb(III) into magadiite and characterization of Tb-intercalated magadiites

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Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

Cited by 14 publications

References 36 publications

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal–Organic Framework Materials

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal–Organic Framework Materials

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb)

Intercalation of Tb(III) into magadiite and characterization of Tb-intercalated magadiites

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Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C₁₅H₉O₅)₃(H₂O)₃]_n (Ln = Eu, Tb)