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Bipyridine-based nanosized metal-organic framework with tunable luminescence by a postmodification with Eu(III): an experimental and theoretical study

(2013) JOURNAL OF PHYSICAL CHEMISTRY C. 117(21). p.11302-11310
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Center for nano- and biophotonics (NB-Photonics)
Abstract
A gallium 2,2'-bipyridine-5,5'-dicarboxylate metal-organic framework, Ga(OH)(bpydc), denoted as COMOC-4 (COMOC = Center for Ordered Materials, Organometallics and Catalysis, Ghent University) has been synthesized via solvothermal synthesis procedure. The structure has the topology of an aluminum 2,2'-bipyridine-5,5'-dicarboxylate - the so-called MOF-253. TEM and SEM micrographs show the COMOC-4 crystals are formed in nanoplates with uniform size of 30-50 nm. The UV-vis spectra of COMOC-4 in methanol solution show maximal electronic absorption at 307 nm. This results from linker to linker transitions as elucidated by time-dependent density functional theory simulations on the linker and COMOC-4 cluster models. When excited at 400 nm, COMOC-4 displays an emission band centered at 542 nm. Upon immersion in different solvents, the emission band for the framework is shifted in the range of 525-548 nm depending on the solvent. After incorporating Eu3+ cations, the emission band of the framework is shifted to even shorter wavelengths (505 nm). By varying the excitation wavelengths from 250 to 400 nm, we can fine-tune the emission from red to yellowish green in the CIE diagram. The luminescence behavior of Eu3+ cations is well preserved and the solid-state luminescence lifetimes of tau(1) = 45 mu s (35.4%) and tau(2) = 162 mu s (64.6%) are observed.
Keywords
coordination polymer, porous materials, post-synthetic modification, ab initio simulations, lanthanide, DENSITY-FUNCTIONAL THEORY, EXCITED-STATES, COORDINATION POLYMERS, LARGE MOLECULES, COMPLEXES, EXCHANGE, LIGAND, SITES, 2, 2'-BIPYRIDINE, 2-BIPYRIDINE

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Citation

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Chicago
Liu, Ying-Ya, Roel Decadt, Thomas Bogaerts, Karen Hemelsoet, Anna Kaczmarek, Dirk Poelman, Michel Waroquier, Veronique Van Speybroeck, Rik Van Deun, and Pascal Van Der Voort. 2013. “Bipyridine-based Nanosized Metal-organic Framework with Tunable Luminescence by a Postmodification with Eu(III): An Experimental and Theoretical Study.” Journal of Physical Chemistry C 117 (21): 11302–11310.
APA
Liu, Y.-Y., Decadt, R., Bogaerts, T., Hemelsoet, K., Kaczmarek, A., Poelman, D., Waroquier, M., et al. (2013). Bipyridine-based nanosized metal-organic framework with tunable luminescence by a postmodification with Eu(III): an experimental and theoretical study. JOURNAL OF PHYSICAL CHEMISTRY C, 117(21), 11302–11310.
Vancouver
1.
Liu Y-Y, Decadt R, Bogaerts T, Hemelsoet K, Kaczmarek A, Poelman D, et al. Bipyridine-based nanosized metal-organic framework with tunable luminescence by a postmodification with Eu(III): an experimental and theoretical study. JOURNAL OF PHYSICAL CHEMISTRY C. 2013;117(21):11302–10.
MLA
Liu, Ying-Ya, Roel Decadt, Thomas Bogaerts, et al. “Bipyridine-based Nanosized Metal-organic Framework with Tunable Luminescence by a Postmodification with Eu(III): An Experimental and Theoretical Study.” JOURNAL OF PHYSICAL CHEMISTRY C 117.21 (2013): 11302–11310. Print.
@article{3235334,
  abstract     = {A gallium 2,2'-bipyridine-5,5'-dicarboxylate metal-organic framework, Ga(OH)(bpydc), denoted as COMOC-4 (COMOC = Center for Ordered Materials, Organometallics and Catalysis, Ghent University) has been synthesized via solvothermal synthesis procedure. The structure has the topology of an aluminum 2,2'-bipyridine-5,5'-dicarboxylate - the so-called MOF-253. TEM and SEM micrographs show the COMOC-4 crystals are formed in nanoplates with uniform size of 30-50 nm. The UV-vis spectra of COMOC-4 in methanol solution show maximal electronic absorption at 307 nm. This results from linker to linker transitions as elucidated by time-dependent density functional theory simulations on the linker and COMOC-4 cluster models. When excited at 400 nm, COMOC-4 displays an emission band centered at 542 nm. Upon immersion in different solvents, the emission band for the framework is shifted in the range of 525-548 nm depending on the solvent. After incorporating Eu3+ cations, the emission band of the framework is shifted to even shorter wavelengths (505 nm). By varying the excitation wavelengths from 250 to 400 nm, we can fine-tune the emission from red to yellowish green in the CIE diagram. The luminescence behavior of Eu3+ cations is well preserved and the solid-state luminescence lifetimes of tau(1) = 45 mu s (35.4\%) and tau(2) = 162 mu s (64.6\%) are observed.},
  author       = {Liu, Ying-Ya and Decadt, Roel and Bogaerts, Thomas and Hemelsoet, Karen and Kaczmarek, Anna and Poelman, Dirk and Waroquier, Michel and Van Speybroeck, Veronique and Van Deun, Rik and Van Der Voort, Pascal},
  issn         = {1932-7447},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY C},
  keyword      = {coordination polymer,porous materials,post-synthetic modification,ab initio simulations,lanthanide,DENSITY-FUNCTIONAL THEORY,EXCITED-STATES,COORDINATION POLYMERS,LARGE MOLECULES,COMPLEXES,EXCHANGE,LIGAND,SITES,2,2'-BIPYRIDINE,2-BIPYRIDINE},
  language     = {eng},
  number       = {21},
  pages        = {11302--11310},
  title        = {Bipyridine-based nanosized metal-organic framework with tunable luminescence by a postmodification with Eu(III): an experimental and theoretical study},
  url          = {http://dx.doi.org/10.1021/jp402154q},
  volume       = {117},
  year         = {2013},
}

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