期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 24, 页码 3866-3874出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201200256
关键词
Chelates; Luminescence; NMR spectroscopy; Terpyridine; UV; Vis spectroscopy
资金
- Czech Science Foundation [P108/12/1143]
- Science Foundation of Charles University [157810]
- Ministry of Education of the Czech Republic [MSM0021620857]
The complexation of terpyridine (tpy) and its 4'-ethynyl (E) and 4'-(2-thienyl) (T) derivatives, as promising chelate end groups for oligomeric components of conjugated metallosupramolecular polymers, with Zn2+ and Fe2+ ions as ion couplers was investigated in acetonitrile using NMR and UV/Vis spectroscopy. The binding of these ligands with Zn2+ ions shows two distinct steps with comparable binding constants in the range of 106 dm3?mol1, whereas their binding with Fe2+ ions shows a strong tendency to form [FeL2]2+ species, which almost do not dissociate to monoligand species [FeL]2+ even at a twofold excess of Fe2+ ions. The ligand exchange dynamics between [ZnL2]2+ species in solution was studied by NMR spectroscopy and the related parameters were determined. UV/Vis spectra taken during complexation show an apparent isosbestic point at 310?+/-?10 nm, and those of the systems with Fe2+ ions also show a metal-to-ligand charge-transfer band at 550580 nm. 4'-Substituents strongly enhance the luminescence of tpy (ca. 400 times). Additional enhancement is provided by binding the ligands to Zn2+ ions, whereas their binding to Fe2+ ions quenches the fluorescence.
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