Gözenekli malzemelerde Pr(III) iyonlarının anten etkisi ile duyarlılaştırılması

Metal organik çerçeveler (MOÇ) genellikle ligandlar ve metal iyonları ile oluşturulan gözenekli malzemelerdir. Son zamanlarda, Ln(III) komplekslerinin fotolüminesans özellikleri alanında yapılan çalışmaların çoğu Eu(III), Tb(III), Dy(III) ve Sm(III) komplekslerine odaklanmıştır. Araştırmalarımıza göre; özellikle Pr(III) komplekslerinin lüminesans özelliklerinin incelenmesi üzerine yapılan çalışmalar literatürde sınırlıdır. Bu çalışmada, metal organik çerçeve elde etmek için Pr(III) metal iyonu seçilmiştir. f-f geçişlerinin yasaklı olması nedeniyle, lantanit (III) iyonlarının doğrudan uyarılması hemen hemen mümkün değildir. Organik ligandların sağladığı anten etkisiyle lüminesans artışı daha etkili bir şekilde elde edilir. Uygun bir ligandın seçimi veya anlamlı tasarımı, mükemmel lüminesans özelliklerini elde etmek için 3 boyutlu MOÇ'lerin oluşturulmasında önemli bir rol oynamaktadır. Bu çalışmada Pr-MOÇ kompleksinin hem görünür hem de NIR bölgedeki lüminesans karakteristiği ile enerji transfer mekanizması incelenmiştir.

Sensitization of Pr(III) ions in porous material via an antenna effect

Metal organic frameworks (MOF) are porous materials which generally construct with ligands and metal ions. Recently, most of studies in the field of photoluminescence properties of Ln(III) complexes has been focused on Eu(III), Tb(III), Dy(III) and Sm(III) compounds. In according to our research; investigation of luminescence properties of specially Pr(III) complexes are limited report in literature. In this study, Pr(III) metal ion has been selected to form the metal organic frameworks. Because of forbidden f–f transitions, direct excitation of lanthanide (III) ions is nearly impossible. The sensitization of organic ligands is more effectively achieved a via antenna effect. To obtain excellent luminescence properties, the significant design or selection of a suitable ligand play a key role in the building of 3D-MOFs. In this work, luminescence characteristics of the Pr-MOF complex both in visible and NIR region and energy transfer mechanism have been investigated.

Keywords:

Metal organic framework, porous material, praseodymium(III), photoluminescence antenna effect,

PDF

___

[1] Stock, N. and Biswas, S., Synthesis of MetalOrganic Frameworks ( MOFs): routes to various MOF topologies, morphologies, and composites, Chemical Review, 112, 933– 969, (2012).
[2] Lincke, J., Lässig, D., Moellmer, J., Reichenbach, C., Puls, A., Moeller, A., Gläser, R., Kalies, G., Staudt, R. and Krautscheid H., A novel copper-based MOF material: Synthesis , characterization and adsorption studies, Microporous Mesoporous Material, 142, 62–69, (2011).
[3] Volkringer, C., Loiseau, T., Guillou, N., Férey, G., Haouas, M., Taulelle, F., Elkaim, E. and Stock, N., High-throughput aided synthesis of the porous metal- organic framework- type aluminum pyromellitate, MIL- 121, with extra Carboxylic Acid functionalization, Inorganic Chemistry, 49, 21, 9852–9862, (2010).
[4] Tabatabaee, M., Sharif, M.A., Vakili, F. and Saheli, S., Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum(III) with benzene- 1, 2, 4, 5- tetracarboxylic acid and 4, 4′- bipyridine, Journal of Rare Earths, 27, 356–361, (2009).
[5] Qi, Y., Wang, Y., Hu, C., Cao, M., Mao, L. and Wang E., A new type of single- helix coordination polymer with mixed ligands, Inorganic Chemistry, 42, 25, 8519–8523, (2003).
[6] Gu, Z.G., Liu, Y.T., Hong, X.J., Zhan, Q.G., Zheng, Z.P., Zheng, S.R., Li, W.S., Hu, S.J. and Cai, Y.P., Construction of metalimidazole- based dicarboxylate networks with topological diversity: thermal stability, gas adsorption, and fluorescent emission properties, Crystal Growth Design, 12, 2178−2186, (2012).
[7] Vilela, S.M.F., Ananias, D., Fenandes, J.A., Silva, P., Gomes, A.C., Silva, N.J.O., Rodrigues, M.O., Tomé, J.P.C., Valante, A.A., Claro, P.R., Carlos, L.D., Rocha, J. and Paz F.A.A., Multifunctional micro- and nanosized metal– organic frameworks assembled from bisphosphonates and lanthanides, Journal of Materials Chemistry C, 2, 3311–3327, (2014).
[8] Yang, Y.S., Liu, M., Yang, Y.P., Jin, Q.H., Li, Z.F., Xue X.N., Zhang, Z.J. and Zheng, W.J., Synthesis, structures, luminescence and terahertz time-domain spectroscopy of seven lanthanide complexes with tetrakis(Oisopropyl)methylenediphosphonate and 1, 10- phenanthroline, Polyhedron, 93, 66–75, (2015).
[9] Xiaoyong, T., Shantang, Y., Ping, L., Ning, W. and Yingliang L., Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd2[C6(COO)6] (H2O)6} and {Ho2[C6(COO)6](H2O)6}, Journal of Rare Earths, 26, 6, 800–803, (2008).
[10] Guo, L., Wu, G. and Li H.H., Synthesis, crystal structures, thermal and luminescent properties of rare earth metal complexes with 1, 2, 4, 5- Benzenetetracarboxylic Acid, Journal of Chemical Crystallography, 42, 192–198, (2012).
[11] Sheldrick, G.M., Acta Crystallography, Section A, 64 , 112, (2008).
[12] Dolomanov, O.V., Bourhis, L.J., Gildea, R.J., Howard, J.A.K., Puschmann, H.J. Applied Crystallography, 42, 339 (2009).
[13] Spek, A.L., Acta Crystallography, Section D, 65, 148, (2009).
[14] MERCURY 1.4.2, Copyright from Cambridge Crystallography Data Center, (2001–2007).
[15] Wang, J.L., Hou, K.L., Xing, Y.H., Deng, Z.Y. and Shi, Z., Synthesis and characterization of two 3-D polymeric lanthanide complexes constructed from 1, 2, 4, 5-benzenetetracarboxylic acid, Journal of Coordination Chemistry, 64, 21, 3767– 3780, (2011).
[16] Wang, J.L., Hou, K.L., Bai, F.Y., Xing, Y.H. and Shi Z., 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, 275–285 (2012).
[17] Acar, Y., Photoluminescence properties of Gd(III) and Ce(III) lanthanide based metal organic frameworks, Anadolu University Journal Of Science And Technology A - Applied Sciences and Engineering, 17, 4, 754–765 (2016).
[18] Marques, L.F., Correa, C.C., Garcia, H.C., Francisco, T.M., Ribeiro, S.J.L., Dutra, J.D.L., Freire, R.O. and Machado, F.C., Theoretical and experimental spectroscopic studies of the first highly luminescent binuclear hydrocinnamate of Eu (III), Tb (III) and Gd (III) with bidentate 2, 2’- bipyridine ligand, Journal of Luminencence, 148, 307– 316 (2014).
[19] Zhou, X., Zhao, X., Wang, Y., Wu, B., Shen, J., Li, L. and Li, Q., Eu (III) and Tb (III) complexes with the nonsteroidal antiinflammatory drug Carprofen: Synthesis, crystal structure and photophysical properties, Inorganic Chemistry, 53, 12275−12282, (2014).
[20] Li, X.L., Chen, C.L., Kang, J.L., Wang, A.L., Wang, P.Y. and Xiao, H.P., Synthesis, crystal structures and near-infrared luminescent properties of three lanthanide-based enantiomeric pairs, Inorganica Chimica Acta, 408, 78–83, (2013).
[21] Chandra, D., Kasture, M.W. and Bhaumik, A., A new microporous MOF material based on Zn (II) -polycarboxylate coordination polymer synthesized with the aid of 1, 6- diaminohexane as template, Microporous and Mesoporous Material, 116, 204–209, (2008).
[22] Jiang, Y.S., Yu, Z.T., Liao, Z.L., Li, G.H. and Chen, J.S., Syntheses and photoluminescent properties of two uranyl- containing compounds with extended structures, Polyhedron, 25, 1359–1366, (2006).
[23] Zhang, Y., Ji, J., Fu, J.D., Cheng, J.W. and Wen, Y.H., Cooperative assembly of coexistent lanthanide– carboxylate chain and layer in a (4, 6) - connected network, Inorganic Chemistry Communications, 35, 181–185, (2013).
[24] Saha, R., Goswami, S., Biswas, S., Seele, I.M., Dey, K., Jana, A.D. and Kumar S., A dynamic metal– organic supramolecular host based on weak p- stacking interactions incorporating 2D water- chloride- methanolic supramolecular sheet, Inorganica Chimica Acta A , 423, 123–132, (2014).
[25] Dang, S., Yu, J., Yu, J., Wang, X., Sun, L., Feng, J., Fan, W. and Zhang, H., Novel Holmium (Ho) and Praseodymium (Pr) ternary complexes with fluorinated- ligand and 4, 5- diazafluoren- 9- one, Material Letters, 65, 1642–1644, (2011).
[26] Sun, L., Qiu, Y., Liu, T., Zhang, J.Z., Dang, S., Feng, J., Wang, Z., Zhang, H. and Shi L., Near infrared and visible luminescence from xerogels covalently grafted with lanthanide [Sm3+, Yb3+, Nd3+, Er3+, Pr3+, Ho3+] β- diketonate derivatives using visible light excitation, ACS Applied Material and Interfaces, 5, 9585–9593, (2013).
[27] Sun, L., Qiu, Y., Liu, T., Peng, H., Deng, W., Wang, Z. and Shi, L., Visible-light sensitized sol-gel-based lanthanide complexes (Sm, Yb, Nd, Er, Pr, Ho, Tm): microstructure, photoluminescence study, and thermostability, The Royal Society of Chemistry Advances, 3, 26367–26375, (2013).
[28] Moore, E.G., Samuel, A.P.S. and Raymond, K.N., From antenna to assay: Lessons learned in lanthanide luminescence, Accounts of Chemical Research, 42, 4, 542-552, (2009).
[29] Dang, S., Sun, L.N., Zhang, H.J., Guo, X.M., Li, Z.F., Feng, J., Guo, H.D. and Guo Z.Y., Near-infrared luminescence from sol- gel materials doped with Holmium (III) and Thulium (III) complexes, Journal of Physical Chemistry C , 112, 13240–13247, (2008).
[30] Kawa, M. and Fréchet, J.M.J., Selfassembled lanthanide- cored dendrimer complexes: Enhancement of the luminescence properties of lanthanide ions through site-isolation and antenna effects, Chemistry of Materials, 10, 286–296 (1998).
[31] Coban, M.B., Amjad, A., Aygun, M. and Kara, H., Sensitization of HoIII and SmIII luminescence by efficient energy transfer from antenna ligands: Magnetic , visible and NIR photoluminescence properties of GdIII , HoIII and SmIII coordination polymers, Inorganica Chimica Acta, 455, 25–33 (2017).