Universität zu Köln

Sobieray, Miriam, Gode, Jens, Seidel, Christiane, Poss, Marieke, Feldmann, Claus ORCID: 0000-0003-2426-9461 and Ruschewitz, Uwe ORCID: 0000-0002-6511-6894 (2015). Bright luminescence in lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand. Dalton Trans., 44 (13). S. 6249 - 6260. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1477-9234

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Abstract

Ten new coordination polymers of the general compositions (2)(infinity)[Ln(III)(tfBDC)(NO3)(DMF)(2)]center dot DMF with Ln(III) = Eu3+ (1), Gd3+ (2), Tb3+ (3), Ho3+ (4), Tm3+ (5), (2)(infinity)[Ln(III)(tfBDC)(CH3COO)(FA)(3)]center dot 3FA with Ln(III) = Sm3+ (6), Eu3+ (7) and (2)(infinity)[Ln(III)(tfBDC)(NO3)(DMSO)(2)] with Ln(III) = Ho3+ (8), Er3+ (9) and Tm3+ (10) were synthesized and structurally characterized by X-ray single crystal diffraction (tfBDC(2-) = 2,3,5,6-tetrafluoroterephthalate, DMF = N,N'-dimethylformamide, FA = formamide, DMSO = dimethyl sulfoxide). 1-5 crystallize in the monoclinic space group C2/c with Z = 8, 6 and 7 in P (1) over bar with Z = 2 and 8-10 in Pbca with Z = 8. All crystal structures contain binuclear lanthanide nodes that are connected by 2,3,5,6-tetrafluoroterephthalates (tfBDC(2-)) to form two-dimensional polymeric structural units. Despite this common structural feature the coordination within these binuclear units is quite different in detail, e.g. CN = 9 for 1-7 and CN = 8 for 8-10. The emission spectra of the europium (1, 7) and terbium (3) compounds reveal bright red and green emission in the visible region. The resulting high quantum yields of 53% (1) and 67% (3) at room temperature show that the replacement of organic ligands with C-H groups by perfluorinated ligands leads to compounds with intense emission, as vibrational quenching is reduced. On the other hand, the influence of the coordinating solvent and additional ligands cannot be neglected, as the replacement of DMF by FA and NO3- by CH3COO- in 7 leads to a reduced quantum yield of only 10%. Thermoanalytical investigations show that all compounds are stable up to 100-150 degrees C, before a stepwise release of solvent molecules starts followed by a decomposition of the coordination polymer.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Sobieray, Miriam UNSPECIFIED UNSPECIFIED UNSPECIFIED Gode, Jens UNSPECIFIED UNSPECIFIED UNSPECIFIED Seidel, Christiane UNSPECIFIED UNSPECIFIED UNSPECIFIED Poss, Marieke UNSPECIFIED UNSPECIFIED UNSPECIFIED Feldmann, Claus UNSPECIFIED orcid.org/0000-0003-2426-9461 UNSPECIFIED Ruschewitz, Uwe UNSPECIFIED orcid.org/0000-0002-6511-6894 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-417047
DOI:	10.1039/c4dt03733b
Journal or Publication Title:	Dalton Trans.
Volume:	44
Number:	13
Page Range:	S. 6249 - 6260
Date:	2015
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1477-9234
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language METAL-ORGANIC FRAMEWORKS; EFFECTIVE IONIC-RADII; ADSORPTION SITES; GAS-ADSORPTION; ACID Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/41704