Preparation, Structure, Photoluminescence and Energy Transfer Mechanism of a Novel Holmium Complex
匡汉茂;张转霞;林隆祯;陈华龙;陈文通
a (Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji’an 343009, China)
b (State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China)
c (Key Laboratory of Jiangxi Province for Persistant Pollutants Control and Resources Recycle (Nanchang Hangkong University), Nanchang 330000, China)
Preparation, Structure, Photoluminescence and Energy Transfer Mechanism of a Novel Holmium Complex
a (Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji’an 343009, China)
b (State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China)
c (Key Laboratory of Jiangxi Province for Persistant Pollutants Control and Resources Recycle (Nanchang Hangkong University), Nanchang 330000, China)
A novel holmium complex [Ho(HIA)2(H2O)4(NO3)](NO3)2 (1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system: a = 14.4797(7), b = 12.4768(2), c = 13.3471(5) Å, β = 118.690(4)°, V = 2115.26(13) Å3, C12H16HoN5O17, Mr = 667.23, Z = 4, Dc = 2.095 g/cm3, μ(MoKα) = 3.838 mm–1 and F(000) = 1304. The crystal structure of 1 is characterized by an isolated structure. Solid-state photoluminescence experiment uncovers that it shows yellow light emission. The emission bands are originated from the characteristic emission of the 4f electrons intrashell transition of the 5S2 → 5I8 and 5F5 → 5I8 of the Ho3+ ions. Energy transfer mechanism is explained by the energy level diagram of the Ho3+ ion and the isonicotinic acid ligand. It has remarkable CIE chromaticity coordinates of (0.4929, 0.4632), so it may be a promising color converter for lighting and displays.
A novel holmium complex [Ho(HIA)2(H2O)4(NO3)](NO3)2 (1, HIA = isonicotinic acid) has been synthesized through hydrothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in the C2/c space group of monoclinic system: a = 14.4797(7), b = 12.4768(2), c = 13.3471(5) Å, β = 118.690(4)°, V = 2115.26(13) Å3, C12H16HoN5O17, Mr = 667.23, Z = 4, Dc = 2.095 g/cm3, μ(MoKα) = 3.838 mm–1 and F(000) = 1304. The crystal structure of 1 is characterized by an isolated structure. Solid-state photoluminescence experiment uncovers that it shows yellow light emission. The emission bands are originated from the characteristic emission of the 4f electrons intrashell transition of the 5S2 → 5I8 and 5F5 → 5I8 of the Ho3+ ions. Energy transfer mechanism is explained by the energy level diagram of the Ho3+ ion and the isonicotinic acid ligand. It has remarkable CIE chromaticity coordinates of (0.4929, 0.4632), so it may be a promising color converter for lighting and displays.
This project was supported by the NNSFC (21361013), Jiangxi Provincial Department of Education’s Item of Science and Technology (GJJ170637), the open foundation (20180008) of the State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, and the open foundation (ST201522007)of the Key Laboratory of Jiangxi Province for Persistant Pollutants Control and Resources Recycle (Nanchang Hangkong University)
匡汉茂;张转霞;林隆祯;陈华龙;陈文通. Preparation, Structure, Photoluminescence and Energy Transfer Mechanism of a Novel Holmium Complex[J]. 结构化学, 2019, 38(3): 337-344.
KUANG Han-Mao;ZHANG Zhuan-Xia;LIN Long-Zhen;CHEN Hua-Long;CHEN Wen-Tong. Preparation, Structure, Photoluminescence and Energy Transfer Mechanism of a Novel Holmium Complex. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2019, 38(3): 337-344.
REFERENCES
(1) Kitchen, J. A. Lanthanide-based self-assemblies of 2,6-pyridyldicarboxamide ligands: recent advances and applications as next-generation luminescent and magnetic materials. Coord. Chem. Rev. 2017, 340, 232–246.
(2) Kaur, K.; Singh, K. J.; Anand, V.; Islam, N.; Bhatia, G.; Kalia, N.; Singh, J. Lanthanide (=Ce, Pr, Nd and Tb) ions substitution at calcium sites of hydroxyl apatite nanoparticles as fluorescent bio probes: experimental and density functional theory study. Ceram. Int. 2017, 43, 10097–10108.
(3) Wang, W.; Feng, W.; Du, J.; Xue, W.; Zhang, L.; Zhao, L.; Li, Y.; Zhong, X. Cosensitized quantum dot solar cells with conversion efficiency over 12%. Adv. Mater. 2018, 30, 1705746–1705749.
(4) Picot, A.; Malvolti, F.; Le Guennic, B.; Baldeck, P. L.; Williams, J. A. G.; Andraud, C.; Maury, O. Two-photon antenna effect induced in octupolar europium complexes. Inorg. Chem. 2007, 46, 2659–2665.
(5) Samuel, A. P. S.; Moore, E. G.; Melchior, M.; Xu, J.; Raymond, K. N. Water-soluble 2-hydroxyisophthalamides for sensitization of lanthanide luminescence. Inorg. Chem. 2008, 47, 7535–7544.
(6) Yan, B.; Xu, B. Spectroscopic study on the photophysical properties of lanthanide complexes with long chain mono-docosyl phthalate. J. Fluoresc. 2005, 15, 619–626.
(7) Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal Structure Solution. University of Göttingen, Germany 1997.
(8) Zhang, J. W.; Jiang, Y.; Xie, Y. R.; Chu, J.; Liu, B. Q. Syntheses, structures, photoluminescence, and magnetism of a series of discrete heavy lanthanide complexes based on a tricarboxylic acid. Inorg. Chim. Acta 2016, 453, 257–262.
(9) Kou, F.; Yang, S.; Zhang, L.; Teat, S. J.; Tian, G. Complexation of Ho(III) with tetraalkyl-diglycolamide in aqueous solutions and a solid state compared in organic solutions of solvent extraction. Inorg. Chem. Commun. 2016, 71, 41–44.
(10) Coban, M. B.; Amjad, A.; Aygun, M.; 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. Inorg. Chim. Acta 2017, 455, 25–33.
(11) Li, Y.; Liu, Y.; Gong, P.; Tian, X.; Luo, J.; Zhao, J. Two isonicotinate-bridging lanthanide substituted phosphotungstate hybrids. Inorg. Chem. Commun. 2016, 74, 42–47.
(12) Mu, Z.; Hu, Y.; Ju, G. Luminescence properties of Eu3+ and Ho3+ in Sr2TiO4. J. Rare Earths 2012, 30, 744–747.
(13) Aleksandrovsky, A. S.; Krylov, A. S.; Malakhovskii, A. V.; Voronov, V. N. Luminescence spectra of Ho3+ in distorted parity-breaking HoF63- octahedral. J. Lumin. 2012, 132, 690–692.
(14) Walsh, B. M.; Barnes, N. P.; Di Bartolo, B. On the distribution of energy between the Tm 3F4 and Ho 5I7 manifolds in Tm-sensitized Ho luminescence. J. Lumin. 1997, 75, 89–98.
(15) Krishnan, R.; Thirumalai, J. Up/down conversion luminescence properties of (Na0.5Gd0.5)MoO4:Ln3+ (Ln = Eu, Tb, Dy, Yb/Er, Yb/Tm, and Yb/Ho) microstructures: synthesis, morphology, structural and magnetic investigation. New J. Chem. 2014, 38, 3480–3491.
(16) Barrera, E. W.; Pujol, M. C.; Carvajal, J. J.; Mateos, X.; Sole, R.; Massons, J.; Speghini, A.; Bettinelli, M.; Cascales, C.; Aguilo, M. White light upconversion in Yb-sensitized (Tm, Ho)-doped KLu(WO4)2 nanocrystals: the effect of Eu incorporation. Phys. Chem. Chem. Phys. 2014, 16, 1679–1686.
(17) Zhan, H.; Zhou, Z.; He, J.; Lin, A. Intense red upconversion emission of Yb/Tm/Ho triply-doped tellurite glasses. Appl. Optics 2012, 51, 3091–3095.
(18) Dexter, D. L. A theory of sensitized luminescence in solids. J. Chem. Phys. 1953, 21, 836–850.
(19) Sato, S.; Wada, M. Relations between intramolecular energy transfer efficiencies and triplet state energies in rare earth β-diketone chelates. Bull. Chem. Soc. Jpn. 1970, 43, 1955–1962.
(20) Xu, B.; Yan, B. Photophysical properties of novel lanthanide (Tb3+, Dy3+, Eu3+) complexes with long chain para-carboxyphenol ester p-L-benzoate (L = dodecanoyloxy, myristoyloxy, palmitoyloxy and stearoyloxy). Spectrochim. Acta A 2007, 66, 236–242.
2019, Vol. 38 
