Luminiscencia de un enrejado metal orgánico de plata(I) con ácido piromelítico dopado con terbio(III)
Palabras clave:
Enrejado metal orgánico, plata(I), luminiscencia, terbio(III), estructura cristalina
Resumen
Se sintetizó un polímero de coordinación tipo MOF ([Ag4btec]n), a partir de nitrato de plata(I) y ácido piromelítico (H4btec), mediante un método modificado en el que se precipitó el material. El objetivo de este estudio fue usar este MOF como antena para aumentar la intensidad de emisión del ion Tb3+. Se analizaron las propiedades luminiscentes del MOF, obteniendo sus espectros de absorción, excitación y emisión en estado sólido, y posteriormente se dopó empleando diferentes proporciones estequiométricas de nitrato de terbio(III) pentahidratado. Se caracterizaron los nuevos materiales mediante difracción de rayos X de polvos y monocristal (sólo del MOF), resonancia magnética nuclear de 13C en estado sólido, espectroscopía IR, análisis elemental. El MOF obtenido como polvo microcristalino y el monocristal presentan la misma fase cristalográfica. Mejoró la luminiscencia del ion Tb3+ en el MOF dopado con este ion, siendo la proporción de dopaje más emisiva aquella donde el Tb3+ se encuentra en la proporción molar de 0.4:1.0 (Ln3+:MOF). Esto es relevante ya que al dopar el material se utiliza una mínima cantidad de ion lantánido, haciendo el material más económico.
Citas
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Bogale, R. F., Chen, Y., Ye, J., Yang, Y., Rauf, A., Duan, L., Tian, P., & Ning, G. (2017). Highly selective and sensitive detection of 4-nitrophenol and Fe3+ ion based on a luminescent layered terbium (III) coordination polymer. Sensors and Actuators, B: Chemical, 245, 171–178. https://doi.org/10.1016/j.snb.2017.01.177
Cui, Y., Yue, Y., Qian, G., and Chen, B. (2012). Luminescent functional metal-organic frameworks “Chemical Reviews”, 112(2), 1126–1162. https://doi.org/10.1021/cr200101d
Czaja, A. U., Trukhan, N., and Müller, U. (2009). Industrial applications of metal–organic frameworks. “Chemical Society Reviews”, 38(5), 1284–1293. https://doi.org/10.1039/b804680h
De Oliveira Silva, J. P., Colaço, M. V., De Souza, L. A., Dos Santos, M. V., Pugina, R. S., y Marques, L. F. (2022). Exploring the Intense Lanthanide Luminescence and High Thermal Stability in a New Mixed Eu3+/Tb3+Organic Framework Series for Marking in Gunshot Residues. “Journal of Physical Chemistry C”, 126(38), 16568–16577. https://doi.org/10.1021/acs.jpcc.2c05594
Fernandes, T. A., Costa, I. F. M., Jorge, P., Sousa, A. C., André, V., Cerca, N., and Kirillov, A. M. (2021). Silver(I) Coordination Polymers Immobilized into Biopolymer Films for Antimicrobial Applications. “ACS Applied Materials and Interfaces”, 13(11), 12836–12844. https://doi.org/10.1021/acsami.0c19446
Gao, Y., Zhu, Y., Wang, Y., & Bi, J. (2024). Water-Stable Ln-MOF as a multi-emitting luminescent sensor for the detection of metal ions and pharmaceuticals. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 323, 124915, https://doi.org/10.1016/j.saa.2024.124915
Hou, K. L., Bai, F. Y., Xing, Y. H., Wang, J. L., & Shi, Z. (2011). A novel family of 3D photoluminescent lanthanide-bta-flexible MOFs constructed from 1,2,4,5-benzenetetracarboxylic acid and different spanning of dicarboxylate acid ligands. CrystEngComm, 13(11), 3884–3894. https://doi.org/10.1039/c0ce00707b
Hou, L., Song, Y., Lang, F., Wang, Z., & Wang, L. (2020). Fluorometric determination of Fe3+ and polychlorinated benzenes based on Tb3+-pyromellitic acid coordination polymer. Journal of Industrial and Engineering Chemistry, 90, 145–151. https://doi.org/10.1016/j.jiec.2020.07.006
Hu, M. L., Zhu, N. W., Li, X. H., & Chen, F. (2004). Hydrothermal synthesis and structure of a novel terbium coordination polymer with packing cavities, {[Tb(TCB)1/2(H2TCB) 1/2(H2O)](H2O)2}n (H 2TCB = 1, 2, 4, 5-benzenetetracarboxylic acid). Crystal Research and Technology, 39(6), 505–510. https://doi.org/10.1002/crat.200310218
Jaber F., Charbonnier E., and Faure R. (1997). Crystal structure of a silver(I) complex with the 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid). “Journal of Chemical Crystallography”, 27(7), 397–400.
Karmakar, A., and Li, J. (2022). Luminescent MOFs (LMOFs): recent advancement towards a greener WLED technology. “Chemical Communications”, 58(77), 10768–10788. https://doi.org/10.1039/d2cc03330e
Li M., Shen A., Man D., Hao X., Wang H., Du X., Ma S., Yuan J., Yang Y. (2021) Tb3+-Doped-Ag-MOFs for fluorescent detection of formaldehyde in a novel smartphone platform and its removal applications in milk products and wastewater. “RSC Advances”, 11, 34291-34299.
Peña-Rodríguez, R., Molina-González, J. A., Desirena-Enrriquez, H., Armenta-Jaime, E., Rivera, J. M., y Castillo-Blum, S. E. (2021). Doping of a Zn-MOF with Eu3+and Tb3+for application in the manufacture of a WLED. “Journal of Materials Chemistry C”, 9(44), 15891–15899. https://doi.org/10.1039/d1tc03454e
Peña-Rodríguez, R., Molina-González, J. A., Desirena-Enrriquez, H., RiveraVillanueva, J. M., y Castillo-Blum, S. E. (2019). Tunable luminescence modulation and warm light emission of Zn-MOF (4,4′-bipyridyl and zinc acetate) doped with Eu3+ and Tb3+. “Materials Chemistry and Physics”, 223, 494–502. https://doi.org/10.1016/j.matchemphys.2018.11.017
Pershagen, E., y Borbas, K. E. (2014). Designing reactivity-based responsive lanthanide probes for multicolor detection in biological systems. “Coordination Chemistry Reviews”, 273–274, 30–46. https://doi.org/10.1016/j.ccr.2013.10.012
Poojary, D. M., y Clearfield, A. (1997). Application of X-ray Powder Diffraction Techniques to the Solution of Unknown Crystal Structures. “Accounts of Chemical Research”, 30, 414–422.
Ran, J., Zhao, X., Hu, X., Chen, Y., & Tian, Z. (2021). 3D Tb(III) and Eu(III) coordination polymers with mixed dicarboxylate ligands: Synthesis, structure and luminescence properties. Polyhedron, 194, 114910. https://doi.org/10.1016/j.poly.2020.114910
Schmidbaur, H., y Schier, A. (2015). Argentophilic interactions. “Angewandte Chemie - International Edition”, 54(3), 746–784. https://doi.org/10.1002/anie.201405936
Silva, M. A., de Campos, N. R., Ferreira, L. A., Flores, L. S., Júnior, J. C. A., dos Santos, G. L., Corrêa, C. C., dos Santos, T. C., Ronconi, C. M., Colaço, M. V., Simões, T. R. G., Marques, L. F., and Marinho, M. V. (2019). A new photoluminescent terbium(III) coordination network constructed from 1,2,4,5-benzenetetracarboxylic acid: Synthesis, structural characterization and application as a potential marker for gunshot residues. “Inorganica Chimica Acta”, 495, 118967–118976. https://doi.org/10.1016/j.ica.2019.118967
Sun, D., Cao, R., Bi, W., Weng, J., Hong, M., y Liang, Y. (2004). Syntheses and characterizations of a series of silver-carboxylate polymers. “Inorganica Chimica Acta”, 357(4), 991–1001. https://doi.org/10.1016/j.ica.2003.10.010
Wang, J. L., Hou, K. L., Bai, F. Y., Xing, Y. H., & Shi, Z. (2012). Hydrothermal synthesis, crystal structure, and photoluminescence of novel lanthanide metal organic frameworks constructed from 1,4-benzene-dicarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid as ligands. Structural Chemistry, 23(1), 275–285. https://doi.org/10.1007/s11224-011-9870-4
West, A. R. (1998). Solid State Chemistry and its Applications. John Wiley & Sons.
Wu, M. X., and Yang, Y. W. (2017). Metal–Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy. “Advanced Materials” 29(23)., 1606134 https://doi.org/10.1002/adma.201606134
Xia, C. K., Min, Y. Y., Yang, K., Sun, W., Jiang, D. L., & Chen, M. (2018). Syntheses, Crystal Structures, and Properties of Three Novel Silver-Organic Frameworks Assembled from 1,2,3,5-Benzenetetracarboxylic Acid Based on Argentophilic Interactions. Crystal Growth and Design, 18(4), 1978–1986. https://doi.org/10.1021/acs.cgd.7b01319
Yam, V. W. W. y Lo K. K. W. (1999). Chemical Society Reviews, 28, 323-334.
Zhang, H. Bin, Tian, C. Bin, Wu, S. T., Lin, J. Di, Li, Z. H., & Du, S. W. (2011). Synthesis, structures and physical properties of new 3D lanthanide coordination polymers constructed from 1,2,4,5-benzenetetracarboxylic acid. Journal of Molecular Structure, 985(2–3), 355–360. https://doi.org/10.1016/j.molstruc.2010.11.020
Zhao, X. Y., Wang, J., & Yang, Q. S. (2021). Highly sensitive and selective sensing of ascorbic acid in water with a three-dimensional terbium(III)-based coordination polymer. European Polymer Journal, 160, 110771, https://doi.org/10.1016/j.eurpolymj.2021.110771
Zheng, J., Yu, Y. D., Liu, F. F., Liu, B. Y., Wei, G., and Huang, X. C. (2014). Modulation of argentophilic interactions by bridging amine ligands: Photoluminescence tuneable by excitation energy or temperature. “Chemical Communications”, 50(64), 9000–9002. https://doi.org/10.1039/c4cc01523a
Bogale, R. F., Chen, Y., Ye, J., Yang, Y., Rauf, A., Duan, L., Tian, P., & Ning, G. (2017). Highly selective and sensitive detection of 4-nitrophenol and Fe3+ ion based on a luminescent layered terbium (III) coordination polymer. Sensors and Actuators, B: Chemical, 245, 171–178. https://doi.org/10.1016/j.snb.2017.01.177
Cui, Y., Yue, Y., Qian, G., and Chen, B. (2012). Luminescent functional metal-organic frameworks “Chemical Reviews”, 112(2), 1126–1162. https://doi.org/10.1021/cr200101d
Czaja, A. U., Trukhan, N., and Müller, U. (2009). Industrial applications of metal–organic frameworks. “Chemical Society Reviews”, 38(5), 1284–1293. https://doi.org/10.1039/b804680h
De Oliveira Silva, J. P., Colaço, M. V., De Souza, L. A., Dos Santos, M. V., Pugina, R. S., y Marques, L. F. (2022). Exploring the Intense Lanthanide Luminescence and High Thermal Stability in a New Mixed Eu3+/Tb3+Organic Framework Series for Marking in Gunshot Residues. “Journal of Physical Chemistry C”, 126(38), 16568–16577. https://doi.org/10.1021/acs.jpcc.2c05594
Fernandes, T. A., Costa, I. F. M., Jorge, P., Sousa, A. C., André, V., Cerca, N., and Kirillov, A. M. (2021). Silver(I) Coordination Polymers Immobilized into Biopolymer Films for Antimicrobial Applications. “ACS Applied Materials and Interfaces”, 13(11), 12836–12844. https://doi.org/10.1021/acsami.0c19446
Gao, Y., Zhu, Y., Wang, Y., & Bi, J. (2024). Water-Stable Ln-MOF as a multi-emitting luminescent sensor for the detection of metal ions and pharmaceuticals. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 323, 124915, https://doi.org/10.1016/j.saa.2024.124915
Hou, K. L., Bai, F. Y., Xing, Y. H., Wang, J. L., & Shi, Z. (2011). A novel family of 3D photoluminescent lanthanide-bta-flexible MOFs constructed from 1,2,4,5-benzenetetracarboxylic acid and different spanning of dicarboxylate acid ligands. CrystEngComm, 13(11), 3884–3894. https://doi.org/10.1039/c0ce00707b
Hou, L., Song, Y., Lang, F., Wang, Z., & Wang, L. (2020). Fluorometric determination of Fe3+ and polychlorinated benzenes based on Tb3+-pyromellitic acid coordination polymer. Journal of Industrial and Engineering Chemistry, 90, 145–151. https://doi.org/10.1016/j.jiec.2020.07.006
Hu, M. L., Zhu, N. W., Li, X. H., & Chen, F. (2004). Hydrothermal synthesis and structure of a novel terbium coordination polymer with packing cavities, {[Tb(TCB)1/2(H2TCB) 1/2(H2O)](H2O)2}n (H 2TCB = 1, 2, 4, 5-benzenetetracarboxylic acid). Crystal Research and Technology, 39(6), 505–510. https://doi.org/10.1002/crat.200310218
Jaber F., Charbonnier E., and Faure R. (1997). Crystal structure of a silver(I) complex with the 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid). “Journal of Chemical Crystallography”, 27(7), 397–400.
Karmakar, A., and Li, J. (2022). Luminescent MOFs (LMOFs): recent advancement towards a greener WLED technology. “Chemical Communications”, 58(77), 10768–10788. https://doi.org/10.1039/d2cc03330e
Li M., Shen A., Man D., Hao X., Wang H., Du X., Ma S., Yuan J., Yang Y. (2021) Tb3+-Doped-Ag-MOFs for fluorescent detection of formaldehyde in a novel smartphone platform and its removal applications in milk products and wastewater. “RSC Advances”, 11, 34291-34299.
Peña-Rodríguez, R., Molina-González, J. A., Desirena-Enrriquez, H., Armenta-Jaime, E., Rivera, J. M., y Castillo-Blum, S. E. (2021). Doping of a Zn-MOF with Eu3+and Tb3+for application in the manufacture of a WLED. “Journal of Materials Chemistry C”, 9(44), 15891–15899. https://doi.org/10.1039/d1tc03454e
Peña-Rodríguez, R., Molina-González, J. A., Desirena-Enrriquez, H., RiveraVillanueva, J. M., y Castillo-Blum, S. E. (2019). Tunable luminescence modulation and warm light emission of Zn-MOF (4,4′-bipyridyl and zinc acetate) doped with Eu3+ and Tb3+. “Materials Chemistry and Physics”, 223, 494–502. https://doi.org/10.1016/j.matchemphys.2018.11.017
Pershagen, E., y Borbas, K. E. (2014). Designing reactivity-based responsive lanthanide probes for multicolor detection in biological systems. “Coordination Chemistry Reviews”, 273–274, 30–46. https://doi.org/10.1016/j.ccr.2013.10.012
Poojary, D. M., y Clearfield, A. (1997). Application of X-ray Powder Diffraction Techniques to the Solution of Unknown Crystal Structures. “Accounts of Chemical Research”, 30, 414–422.
Ran, J., Zhao, X., Hu, X., Chen, Y., & Tian, Z. (2021). 3D Tb(III) and Eu(III) coordination polymers with mixed dicarboxylate ligands: Synthesis, structure and luminescence properties. Polyhedron, 194, 114910. https://doi.org/10.1016/j.poly.2020.114910
Schmidbaur, H., y Schier, A. (2015). Argentophilic interactions. “Angewandte Chemie - International Edition”, 54(3), 746–784. https://doi.org/10.1002/anie.201405936
Silva, M. A., de Campos, N. R., Ferreira, L. A., Flores, L. S., Júnior, J. C. A., dos Santos, G. L., Corrêa, C. C., dos Santos, T. C., Ronconi, C. M., Colaço, M. V., Simões, T. R. G., Marques, L. F., and Marinho, M. V. (2019). A new photoluminescent terbium(III) coordination network constructed from 1,2,4,5-benzenetetracarboxylic acid: Synthesis, structural characterization and application as a potential marker for gunshot residues. “Inorganica Chimica Acta”, 495, 118967–118976. https://doi.org/10.1016/j.ica.2019.118967
Sun, D., Cao, R., Bi, W., Weng, J., Hong, M., y Liang, Y. (2004). Syntheses and characterizations of a series of silver-carboxylate polymers. “Inorganica Chimica Acta”, 357(4), 991–1001. https://doi.org/10.1016/j.ica.2003.10.010
Wang, J. L., Hou, K. L., Bai, F. Y., Xing, Y. H., & Shi, Z. (2012). Hydrothermal synthesis, crystal structure, and photoluminescence of novel lanthanide metal organic frameworks constructed from 1,4-benzene-dicarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid as ligands. Structural Chemistry, 23(1), 275–285. https://doi.org/10.1007/s11224-011-9870-4
West, A. R. (1998). Solid State Chemistry and its Applications. John Wiley & Sons.
Wu, M. X., and Yang, Y. W. (2017). Metal–Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy. “Advanced Materials” 29(23)., 1606134 https://doi.org/10.1002/adma.201606134
Xia, C. K., Min, Y. Y., Yang, K., Sun, W., Jiang, D. L., & Chen, M. (2018). Syntheses, Crystal Structures, and Properties of Three Novel Silver-Organic Frameworks Assembled from 1,2,3,5-Benzenetetracarboxylic Acid Based on Argentophilic Interactions. Crystal Growth and Design, 18(4), 1978–1986. https://doi.org/10.1021/acs.cgd.7b01319
Yam, V. W. W. y Lo K. K. W. (1999). Chemical Society Reviews, 28, 323-334.
Zhang, H. Bin, Tian, C. Bin, Wu, S. T., Lin, J. Di, Li, Z. H., & Du, S. W. (2011). Synthesis, structures and physical properties of new 3D lanthanide coordination polymers constructed from 1,2,4,5-benzenetetracarboxylic acid. Journal of Molecular Structure, 985(2–3), 355–360. https://doi.org/10.1016/j.molstruc.2010.11.020
Zhao, X. Y., Wang, J., & Yang, Q. S. (2021). Highly sensitive and selective sensing of ascorbic acid in water with a three-dimensional terbium(III)-based coordination polymer. European Polymer Journal, 160, 110771, https://doi.org/10.1016/j.eurpolymj.2021.110771
Zheng, J., Yu, Y. D., Liu, F. F., Liu, B. Y., Wei, G., and Huang, X. C. (2014). Modulation of argentophilic interactions by bridging amine ligands: Photoluminescence tuneable by excitation energy or temperature. “Chemical Communications”, 50(64), 9000–9002. https://doi.org/10.1039/c4cc01523a
Publicado
2026-08-26
Sección
Artículos de Investigación
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