Evropiyum içeren lüminesans özelliği gösteren metal-organik malzemelerin üretimi ve yapılarının araştırılması

Öz

Molekül yapılarında birleştirici olarak ligand ve bağlayıcı olarak metal merkezler bulunan, uzaysal mimarisi özgün olan Metal organik çerçevelerin (MOÇ), moleküller arası uzaklıkları büyük olduğundan geniş hacimli boşluklara sahip olma özelliği ve yüzey alanlarının geniş olması nedeniyle manyetizma, lüminesans, hidrojen depolama, gaz absorbsiyonu, optik sensör gibi bir çok fiziksel/kimyasal/elektro-optik uygulama alanları mevcuttur.

 

Bu çalışmada; Lantanit Metal Organik Çerçeveler içeren; [Eu(2-STP)], [2-STP=2-sülfoterefitalat] (1) hidrotermal yöntem ile sentezlenmiştir. Sentezlenen bu malzemenin yapısal analizi; Toz kristal X-ışını kırınımı, katı hal UV ve FT-IR spektroskopisi teknikleri kullanılarak açığa çıkartılmıştır. Malzemenin katı hal fotolüminesans özellikleri oda sıcaklığında görünür bölge ve yakın kızıl ötesi bölgede ölçülmüş ve “anten” görevi yapan 2-STP ligandın dan Eu^III iyonuna enerji transfer mekanizması detaylı olarak tartışılmıştır.

 

Anahtar Kelimeler

• MOÇ,lüminesans,Evropiyum

Synthesis and structural analysis of europium metal-organic materials which show luminescence properties

Öz

Metal organic frameworks (MOFs), which is unique in spatial architecture and has ligands and metal centers as linkers and as a binding in molecular structures, due to their large intermolecular distances and their large surface area, they have many physical/chemical/electro-optic application areas such as magnetism, luminescence, hydrogen storage, gas absorption, optical sensor and so on.

 

In this work; Lanthanide Metal Organic Frameworks; [Eu(2-STP)], (2-STP = 2-sulfoterephthalate) (1) were synthesized using hydrothermal method. The structural analysis of synthesized material has been characterized by powder X-ray diffraction, solid state UV and FT-IR spectra. The solid state photoluminescence properties of the material were measured at room temperature in visible and NIR region, and the energy transfer mechanism from 2-STP ligand to the central Eu^III ion via an ‘‘antenna effect” was discussed in details.

Anahtar Kelimeler

• MOF,luminescence,Europium

Kaynakça

1. Zhao, B., Chen, X.Y., Cheng, P., Liao, D.Z., Yan, S.P. ve Jiang, Z.H., Coordination polymers containing 1D channels as selective luminescent probes, Journal of Amarican Chemical Society, 126, 15394–15395, (2004).
2. Guo, Z.Y., Wu, H., Srinivas, G., Zhou, Y.M., Xiang, S.C., Chen, Z.X., Yang, Y. T., Zhou, W., O'Keeffe, M. ve Chen, B.L., A metal–organic framework with optimized open metal sites and pore spaces for high methane storage at room temperature, Angewandte Chemie International Edition, 50, 3178–3181, (2011).
3. Jiang, C.Y., Wu, T., Zheng, S.T., Zhao, X., Lin, Q.P., Bu, X.H. ve Feng, P.Y., A nine–connected mixed–ligand nickel–organic framework and its gas absorption properties, Crystal Growth & Design, 11, 3713–3716, (2011).
4. Getman, R.B., Bae, Y.S., Wilmer, C.E. ve Snurr, R.Q., Review and analysis of molecular simulations of methane, hydrogen, and acetylene storage in metal–organic frameworks, Chemical Reviews, 112, 703–723, (2012).
5. Bao, S.S., Ma, L.F., Wang, Y., Fang, L., Zhu, C.J., Li, Y.Z. ve Zheng, L.M., Anion–directed self–assembly of lanthanide–notp compounds and their fluorescence, magnetic, and catalytic properties, Chemistry – A European Journal, 13, 2333–2343, (2007).
6. Lin, Z.J., Yang, Z., Liu, T.F., Huang, Y.B. ve Cao, R., Microwave–assisted synthesis of a series of lanthanide metal–organic frameworks and gas absorption properties. Inorganic Chemistry, 51, 1813–1820, (2012).
7. Çoban, M.B., Erkarslan, U., Oylumluoglu, G., Aygün, M. ve Kara, H., Hydrothermal synthesis, crystal structure and photoluminescent properties; 3D Holmium(III) coordination polymer, Inorganica Chimica Acta, 447, 87-91, (2016).
8. Çoban, M.B., Amjad, A., Aygun, M. ve 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).

9. De Sa´, G.F., Malta, O.L., de Mello D.C., Simas, A.M., Longo, R.L., Santa-Cruz P.A. ve de Silv, E.F., Spectroscopic properties and design of highly luminescent lanthanide coordination complexes, Coordination Chemistry Reviews, 196, 165–195, (2000).
10. Wang, Z., Streobele, M., Zhang, K.L., Meyer H.J., You, X.Z. ve Yu, Z., A new family of two-dimensional lanthanide(III) coordination polymers: synthesis, structures and properties of [Ln(SIP)(H2O)4]n (Ln=Eu, Gd, Ce, and NaH2SIP=5-sulfoisophthalic acid monosodium salt), Inorganic Chemistry Communications, 5, 230–234, (2002).
11. Hua-Bin, Z., Chong-Bin, T., Shu-Ting, W., Jian-Di L., Zhi-Hua, L. ve Shao-Wu, D., Synthesis, structures and physical properties of new 3D lanthanide coordination polymers constructed from 1,2,4,5-benzenetetracarboxylic acid, Journal of Molecular Structure, 985, 355-360, (2011).
12. Li-Juan, H., Ya-Jie, K., Ning, S. ve Xing-Ling, J., A new europium fluorous metal-organic framework with pentafluorobenzoate and 1,10-phenanthroline ligands: Synthesis, structure and luminescent properties, Journal of Flourino Chemistry, 166, 122-126, (2014).
13. Hui, B., Zhenting, W. ve Ming, H., Lanthanide metal–organic frameworks with 2,2-bipyridinepolycarboxylic acid: Synthesis, crystal structures and fluorescent properties, Inorganica Chimica Acta, 427, 112-117, (2015).
14. Yi-Xia, R., Miao, A., Hong-Mei, C., Mei-Li, Z. ve Ji-Jiang, W., Cooperation of coordinative and π••π interaction in directing two-fold interpenetrated architecture of two Eu/Dy(III) 2-sulfoterephthalate complexes with 4,4-bipyridine, Zeitschrift für Anorganische und Allgemeine Chemie, 641, (3-4), 525–528, (2015).
15. Hong-Ping, X., You-Xuan, Z., Xiao-Qiang, L., Jing-Lin, Z. ve Xiao-Zeng, Y., Hydrothermal synthesis, crystal structures, and luminescent properties of two lanthanide (III) complexes containing 2-sulfoterephthalate, Journal of Molecular Structure, 888, 55-61, (2008).
16. Lyszczek, R.M., Thermal investigations of cefadroxil complexes with transition metals, Journal of Thermal Analysis and Calorimetry, 78, 473, (2004).
17. Li, X., Lu, Y., Bing, Y. ve Zha, M-Q., Synthesis, photoluminescent, and magnetic properties of two lanthanide sulfosalicylate complexes, Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 42, 698–704, (2012).
18. Li, X., Xie, Z., Lin, J. ve Cao, R., Lanthanide-organic frameworks constructed from multi-functional ligands: Syntheses, structures, near-infrared and visible photoluminescence properties, Journal of Solid State Chemistry, 182, 2290–2297, (2009).
19. Feng, X., Feng, Y.Q., Chen, J., Ng, S.W., Wang, L.Y. ve Guo, J.Z., Reticular three-dimensional 3d–4f frameworks constructed through substituted imidazole-dicarboxylate: syntheses, luminescence and magnetic properties study, Dalton Transactions, 44, 804–816, (2015).
20. Lever, A.B.P., Inorganic electronic spectroscopy, Amsterdam, The Netherlands: Elsevier, (1984).