ÖZGÜN Ho(5-SSA), (5-SSA = 5-SÜLFOSALİSİLİK ASİT) KAFES YAPISININ SENTEZLENMESİ VE OPTİKSEL ÖZELLİKLERİ

Öz

Birleştirici olarak adlandırılan organik yapıdaki ligandlar ile bağlayıcı olarak sınıflandırılan metal merkezlerin oluşturdukları mükemmel özgün mimariye sahip olan süngerimsi yapılar diğer bir deyişle Metal organik çerçeveler (MOÇ) üzerinde son yıllarda oldukça yoğun çalışmalar yapılmaktadır. Bu yoğunlaşmanın başlıca nedeni bu tür malzemelerin sensörler, gaz depolama, foto-katalizörler, organik ışık yayan diyotlar (OLED), güneş hücreleri (SC) ve lüminesans yayabilen aygıtlar gibi birçok teknolojik uygulama alanlarında kullanılabilme potansiyelinin yüksek olmasından ötürüdür. Metal organik çerçevelerin özellikleri, seçilen organik ligandlara ve metal iyonlarına bağlıdır. Dolayısıyla özgün olarak sentezlenebilen bu kristal malzemeler ile yeni araştırma ve teknoloji geliştirme (Ar-Te-Ge) alanları keşfedilebilmektedir. Bu çalışmada, Ho(III)-tabanlı metal-organik çerçevesi (Ho-MOÇ; [Ho(5-SSA)], 5-SSA = 5-Sülfosalisilik asit) hidrotermal metot ile sentezlenmiştir. Toz kristal X-ışını kırınımı, oda sıcaklığında katı-hal UV ve FT-IR spektroskopisi teknikleri yardımıyla yapısal karakterizasyonu yapılmıştır. Buna ek olarak, oda sıcaklığında görünür ve yakın kızıl ötesi (NIR) bölgede katı hal fotolüminesans ölçümleri alınmış ve 5-SSA ligandından Ho+3 iyonuna olan enerji transfer mekanizması detaylı bir şekilde incelenmiştir.  UV ışınım altında (349 nm’de), 5-SSA ligandı geniş bir lacivert renginde yayılım sergilerken, Ho-MOÇ kompleksi UV-Görünür ve NIR bölgesinde Ho+3 iyonunun çeşitli karakteristik emisyonlarını sergilemiştir. Mükemmel ışıldama performansları, bu bileşiği yüksek verimli ışınım veren malzemeler için çok iyi bir aday haline getirmektedir. 

Anahtar Kelimeler

• Lüminesans,Metal-Organik Çerçeveler,Holmiyum

SYNTHESIS AND OPTICAL PROPERTIES OF THE NOVEL Ho(5-SSA), (5-SSA = 5-SULFOSALICYLIC ACID) CAGE STRUCTURE

Öz

In recent years, intensive studies have been made on metal-organic frameworks (MOFs) which is kind of spongy structures having excellent original architectures formed by ligands in organic forms and metal centers classified as binders. The main reason for this condensation is due to the great huge potential for such materials to be used in many technological application areas such as sensors, gas storage, photo-catalysis, organic light emitting diodes (OLEDs), solar cells (SCs) and luminescent emitting devices. The properties of the metal-organic frameworks depend on the selected organic ligands and metal ions. Therefore, new research and technology development (R-T-G) fields can be discovered with these materials that can be originally synthesized. In this work, Ho(III)-based metal-organic framework (Ho-MOF; [Ho(5-SSA)], 5-SSA = 5-sulfosalicylic acid) was synthesized by hydrothermal method. The structural characterization has been made by powder X-ray diffraction, a room temperature solid-state UV and FT-IR spectroscopy. In addition, the solid-state photoluminescence measurements have been taken at room temperature in the UV-visible and near-infrared region (NIR) and the energy transfer mechanism from 5-SSA ligand to the Ho+3 ion is investigated in detail. Under the excitation of UV light (at 349 nm), 5-SSA ligand exhibited a broad navy-blue emission while its Ho-MOF complex exhibited several characteristic emissions of the Ho+3 ion in the UV-Visible and NIR region. The excellent luminescent performances make this compound very good candidate for efficient luminescence materials.

Anahtar Kelimeler

• Luminescence,Metal-Organic Frameworks,Holmium

Kaynakça

1. Nevruzoglu, V., Demir, S., Karaca, G., Tomakin, M., Bilgin, N., and Yılmaz, F., "Improving the Stability of Solar Cells Using Metal-Organic Frameworks", Journal of Materials Chemistry A, 4, 7930–7935, 2016.
2. He, Y., Krishna, R., and Chen, B., "Metal–organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons", Energy & Environmental Science, 5, 9107–9120, 2012.
3. Li, S., and Xu, Q., "Metal–organic frameworks as platforms for clean energy", Energy & Environmental Science, 6, 1656–1683, 2013.
4. Vikrant, K., Kumar, V., Kim, K., and Kukkar, D., "Metal–organic frameworks (MOFs): potential and challenges for capture and abatement of ammonia", Journal of Materials Chemistry A, 5, 22877–22896, 2017.
5. Gunatilleke, W. D. C. B., Wei, K., Niu, Z., Wojtas, L., Nolas, G., and Ma, S., "Thermal conductivity of a perovskite-type metal–organic framework crystal", Dalton Transactions, 46, 13342–13344, 2017.
6. Li, J., Ma, Y., Mccarthy, M. C., Sculley, J., Yu, J., Jeong, H., et al., "Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks", Coordination Chemistry Reviews, 255, 1791–1823, 2011.
7. Atencio, R., Biradha, K., Hennigar, T. L., Poirier, K. M., Power, K. N., Seward, C. M., et al., "Flexible Bilayer Architectures in the Coordination Polymers [MII(NO3)2(1,2-bis(4-Pyrdiyl)Ethane)1.5]n (MII = Co, Ni)", Crystal Enginnering, 3 (4), 203–212, 1998.
8. Wang, Z., Xiong, R., Foxman, B. M., Wilson, S. R., and Lin, W., "Two- and Three-Dimensional Cadmium Coordination Polymers Based on N , N - ( 2-Pyridyl ) - ( 4-pyridylmethyl ) amine", Inorganic Chemistry, 38, 1523–1528, 1999.

9. Oylumluoglu, G., "4,4- bipiridin ve 2-amino-1,4-benzendikarboksilik asit tabanlı yeni bileşiğin sentezlenmesi ve hidrojen bağlı 3D polimerik yapısı", Journal of Balıkesir Inst. Sci. Technoogy, Online, 1–7, 2018.
10. Sehimi, H., and Zid, M. F., "A novel Mn(II) oxalato-bridged 2D coordination polymer: synthesis, crystal structure, spectroscopic, thermal and magnetic properties", Journal of Chemical Sciences, 130, 1–9, 2018.
11. Shin Won, J., Jeong, A. R., Jeoung, S., Moon, H. R., Komatsumaru, Y., Hayami, S., et al., "Three-dimensional iron(II) porous coordination polymer exhibiting carbon dioxide-dependent spin crossover", Chemical Communications, 54, 4262–4265, 2018.
12. Davarcı, D., "Design and construction of one-dimensional coordination polymers based on the dispiro-dipyridyloxy-cyclotriphosphazene ligand", Polyhedron, 146, 99–107, 2018.
13. Dong, Y., Layland, R. C., Smith, M. D., Pschirer, N. G., Bunz, U. H. F., Loye, H., et al., "Syntheses and Characterizations of One-Dimensional Coordination Polymers Generated from Cadmium Nitrate and Bipyridine Ligands", Inorganic Chemistry, 38, 3056–3060, 1999.
14. Wang, Z., Luo, X., Yun, R., Wang, Z., Huang, L., Hang, C., et al., "Highly Selective Carbon Dioxide Capture and Cooperative Catalysis of a Water-Stable Acylamide-Functionalized Metal- Organic Framework", European Journal of Inorganic Chemistry, 2018, 1309–1314, 2018.
15. Qiu, J., Zhang, X., Feng, Y., Zhang, X., Wang, H., and Yao, J., "Modified metal-organic frameworks as photocatalysts", Applied Catalysis B: Enviromental, 231, 317–342, 2018.
16. Yahsi, Y., Ozbek, H., Aygün, M., and Kara, H., "Crystal structure and photoluminescence properties of a new CdII coordination polymer catena- poly[bis[4-bromo-2-({[2-(pyrrolidin-1-yl)ethyl]- imino}methyl)phenolato-j3N,N000,O]di-l3-chlorido- di-l2-chlorido-bis(methanol-jO)tricadmium(II)]", Acta Crystallographica Section C Structural Chemistry, C72, 426–431, 2016.
17. Li, W., Guo, Y., and Zhang, W., "A porous Cu ( II ) metal-organic framework : Synthesis , crystal structure and gas adsorption properties", Journal of Molecular Structure, 1143, 20–22, 2017.
18. Zhou, H., Liu, B., Wang, H., Hou, L., Zhang, W., and Wang, Y., "Construction of Highly Porous Pillared Metal − Organic Frameworks: Rational Synthesis, Structure, and Gas Sorption Properties", Inorganic Chemistry, 56, 9147–9155, 2017.
19. Cosquer, G., Morimoto, M., Irie, M., Fetoh, A., Breedlove, B. K., and Yamashita, M., "Photo-control of the magnetic properties of Dy(III) and Ho(III) homometal coordination polymers bridged by a diarylethene ligand", Dalton Transactions, 44, 5996–6002, 2015.
20. Li, T., and Xia, J., "Synthesis and Crystal Structure of a Novel Ho ( III ) Coordination Polymer with Oxalic Acid", Advanced Materials Research, 873, 697–700, 2014.
21. Marques, L. F., Correa, C. C., Ribeiro, S. J. L., Molíria, V., Diogo, J., Dutra, L., et al., "Synthesis , structural characterization , luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho ( III ), Gd ( III ) and Eu ( III ) with 2 , 5-thiophenedicarboxylate anion", Journal of Solid State Chemistry, 227, 68–78, 2015.
22. Zhang, Y., and Zheng, J., "Three Ln ( III ) -2 , 3 , 5-trichlorobenzoate coordination polymers ( Ln = Tb , Ho and Er ): Syntheses , structures and magnetic properties", Inorganic Chemistry Communications, 59, 21–24, 2015.
23. Acar, Y., "Photoluminescence Properties of Gd(III) and Ce(III) Lanthanide Based Metal Organic Frameworks", Mühendislik Anadolu University Journal of Science and Technology A-Applied Sciences and Engineering, 17, 754–765, 2016.
24. Dönmez, A., Erkarslan, U., and Karadeniz, Ş., "Evropiyum içeren lüminesans özelliği gösteren metal- organik malzemelerin üretimi ve yapılarının araştırılması", Journal of Balıkesir Inst. Sci. Technoogy, 19, 64–69, 2017.
25. Dönmez, A., Erkarslan, U., and Karadeniz, Ş., "[Eu(1,2,4-BTC)], (1,2,4-BTC=1,2,4- benzen trikarboksilik asit) koordinasyon polimerinin kristal yapı ve optik özelliklerinin araştırılması", Journal of Balıkesir Inst. Sci. Technoogy, 19, 44–49, 2017.
26. Su, S., Wang, S., Song, X., Song, S., Qin, C., Zhu, M., et al., "Syntheses, structures, photoluminescence, and magnetic properties of (3,6)-and 4-connected lanthanide metal–organic frameworks with a semirigid tricarboxylate ligand", Dalton Transactions, 41, 4772–4780, 2012.
27. Zhou, W., Wu, Y., Zhou, Z., Qin, Z., Ye, X., Tian, F., et al., "Construction of a series of lanthanide metal – organic frameworks ( Ln-MOFs ) based on a new symmetrical penta-aromatic carboxylate strut : Structure , luminescent and magnetic properties", Inorganica Chimica Acta, 453, 757–763, 2016.
28. Luo, L.-L., Qu, X.-L., Li, Z., Li, X., and Sun, H.-L., "Isostructural Lanthanide-Based Metal-Organic Frameworks: Structure, Photoluminescence and Magnetic Property", Dalton Transactions, Online, 1–11, 2017.
29. Zhang, H., Peng, Y., Shan, X., Tian, C., and Du, S., "Lanthanide metal organic frameworks based on octahedral secondary building units : Structural , luminescent , and magnetic properties", Inorganic Chemistry Communications, 14, 1165–1169, 2011.
30. Rodenas, T., Luz, I., Prieto, G., Seoane, B., Miro, H., Corma, A., et al., "Metal – organic framework nanosheets in polymer composite materials for gas separation", Nature Materials, 14, 48–55, 2015.
31. Xia, W., Mahmood, A., Zou, R., and Xu, Q., "Metal-Organic Frameworks and their derived nanostructures for Electrochemical Energy Storage and Conversion", Energy & Environmental Science, 8, 1837–1866, 2015.
32. Sun, L., Qiu, Y., Liu, T., Peng, H., Deng, W., Wang, Z., et al., "RSC Advances", RSC Advances, 3, 26367–26375, 2013.
33. Chi, Y., Liu, T., Jin, J., Zhang, G., and Niu, S., "Synthesis , structures and near-infrared luminescence properties of Ho 3 + and Yb 3 + coordination complexes", Journal of Physical and Chemistry of Solids, 74, 1745–1750, 2013.
34. Allendorf, M. D., Bauer, C. A., Bhakta, R. ., and Houk, R. J. ., "CRITICAL REVIEW www.rsc.org/csr | Chemical Society Reviews View Online Luminescent metal–organic frameworks", Chemical Society Reviews, 38, 1330–1352, 2009.
35. Natarajan, S., and Mahata, P., "Metal-Organic Framework Structures – how closely are they related to Classical Inorganic Structures", Chemical Society Reviews, 38, 2304–2318, 2009.
36. Oylumluoglu, G., Burak, M., Kocak, C., Aygun, M., and Kara, H., "2-and 1-D coordination polymers of Dy ( III ) and Ho ( III ) with near infrared and visible luminescence by ef fi cient charge-transfer antenna ligand", Journal of Molecular Structure, 1146, 356–364, 2017.
37. Coban, M. B., Erkarslan, U., Oylumluoglu, G., Aygun, M., and Kara, H., "Hydrothermal synthesis , crystal structure and Photoluminescent properties ; 3D Holmium ( III ) coordination polymer", Inorganica Chimica Acta, 447, 87–91, 2016.
38. Li, X., Lu, Y., Bing, Y., Zha, M., Li, X., Lu, Y., et al., "Synthesis , Photoluminescent , and Magnetic Properties of Two Lanthanide Sulfosalicylate Complexes Two Lanthanide Sulfosalicylate Complexes", Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 3174, 698–704, 2012.
39. Coban, M. B., Amjad, A., Aygun, M., and Kara, H., "Sensitization of Ho III and Sm III luminescence by efficient energy transfer from antenna ligands : Magnetic , visible and NIR photoluminescence properties of Gd III , Ho III and Sm III coordination polymers", Inorganica Chimica Acta, 455, 25–33, 2017.
40. Xiao, H., Zheng, Y., Liang, X., Zuo, J., and You, X., "Hydrothermal synthesis , crystal structures , and luminescent properties of two lanthanide ( III ) complexes containing 2-sulfoterephthalate", Journal of Molecular Structure, 888, 55–61, 2008.
41. Zhang, L., and Zhu, L., "Influence of neutral amine ligands on the network assembly of lead ( II ) 4-sulfobenzoate complexes", Journal of Molecular Structure, 873, 61–68, 2008.
42. Liu, Q., and Xu, L., "Novel Structure Evolution of Lanthanide – SIP Coordination Polymers ( NaH 2 SIP = 5-Sulfoisophthalic Acid Monosodium Salt ) from a 1D Chain to a 3D Network as a Consequence of the Lanthanide Contraction Effect", European Journal of Inorganic Chemistry, 2005, 3458–3466, 2005.
43. Sun, H.-Y., Huang, C.-H., Jın, X.-L., and Xu, G.-X., "The Synthesis, Crystal Structure and Synergistic Florescence Effect of a Heteronuclear Lanthanide Complex (HLC)", Polyhedron, 14, 1201–1206, 1995.
44. Li, X., Xie, Z., Lin, J., and 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.
45. Coban, M. B., "Synthesis and photophysical properties of new Eu ( III ) complex", Journal of Balıkesir Inst. Sci. Technoogy, 19, 7–15, 2017.
46. Zhou, X., Zhao, X., Wang, Y., Wu, B., Shen, J., Li, L., et al., "Eu ( III ) and Tb ( III ) Complexes with the Nonsteroidal Anti- In fl ammatory Drug Carprofen : Synthesis , Crystal Structure , and Photophysical Properties", Inorganic Chemistry, 53, 12275–12282, 2014.
47. Feng, X., Feng, Y., Chen, J. J., Ng, S., Wang, L., and Guo, J., "Reticular three-dimensional 3d–4f frameworks constructed through substituted imidazole-dicarboxylate: syntheses, luminescence and magnetic properties study", Dalton Transactions, 44, 804, 2015.
48. Łyszczek, R., and Mazur, L., "Polynuclear complexes constructed by lanthanides and pyridine-3 , 5-dicarboxylate ligand : Structures , thermal and luminescent properties", Polyhedron, 41, 7–19, 2012.
49. Dang, S., Yu, J., Wang, X., Sun, L., Deng, R., and Feng, J., "NIR-luminescence from ternary lanthanide [ Ho III , Pr III and Tm III ] complexes with 1-(2-naphthyl)-4,4,4-trifluoro-1,3-butanedionate", Journal of Luminescence, 131, 1857–1863, 2011.
50. Dang, S., Sun, L., Zhang, H., Guo, X., Li, Z., Feng, J., et al., "Near-Infrared Luminescence from Sol - Gel Materials Doped with Holmium ( III ) and Thulium ( III ) Complexes", Journal of Physics and Chemistry of Solids, 112, 13240–13247, 2008.
51. Sabbatinia, N., Mecatia, A., Guardiglia, M., Balzania, V., and Lehn, J., "Lanthanide luminescence in supramolecular species", Journal of Luminescence, 49, 463–468, 1991.
52. Dexter, D. L., "A Theory of Sensitized Luminescence in Solids Articles you may be interested in A Theory of Sensitized Luminescence in Solids", The Journal of Chemical Physics, 21, 836–850, 1953.