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Synthesis, structures, and photoluminescence properties of novel lanthanide tetracyanoplatinates lacking Pt-Pt interactions

Journal Article · · Journal of Solid State Chemistry
 [1]
  1. Department of Chemistry, University of South Alabama, 307 University Boulevard, Chemistry Building, Room 223, Mobile, AL 36688 (United States)

The synthesis of a series of lanthanide tetracyanoplatinates all incorporating 2,2':6',2''-terpyridine (terpy) have been carried out by reaction of Ln{sup 3+} nitrate salts with terpy and potassium tetracyanoplatinate. The incorporation of different Ln{sup 3+} cations results in the isolation of [Ln(DMF){sub 2}(C{sub 15}H{sub 11}N{sub 3})(H{sub 2}O){sub 2}(NO{sub 3})]Pt(CN){sub 4} (Ln=La-Nd, Sm-Yb) under otherwise identical reaction conditions. These compounds have been isolated as single crystals and X-ray diffraction has been used to investigate their structural features. All of the reported compounds are isostructural. Crystallographic data for the representative Eu{sup 3+} compound (EuPt) are (MoKalpha, lambda=0.71073 A): monoclinic, space group P2{sub 1}/c, a=10.1234(4) A, b=18.7060(7) A, c=17.1642(5) A, beta=97.249(3){sup o}, V=3224.4(2), Z=4, R(F)=2.78% for 426 parameters with 7724 reflections with I>2sigma(I). The structure consists of a zero-dimensional, ionic salt containing complex [Eu(DMF){sub 2}(C{sub 15}H{sub 11}N{sub 3})(H{sub 2}O){sub 2}(NO{sub 3})]{sup 2+} cations and Pt(CN){sub 4}{sup 2-} anions. The complex cations contain the Eu{sup 3+} ions in a tri-capped trigonal prismatic coordination environment with one terdentate 2,2':6',2''-terpyridine molecule, one bidentate nitrate anion, two O-bound dimethylformamide molecules, and two coordinated water molecules. Photoluminescence data illustrate that EuPt displays intramolecular energy transfer from the coordinated terpy molecule to the Eu{sup 3+} cation. The uncoordinated tetracyanoplatinate anion also exhibits visible emission. - Graphical abstract: The synthesis of an isostructural series of lanthanide tetracyanoplatinates incorporating 2,2':6',2''-terpyridine are presented. Solid-state absorption and luminescence properties are discussed for the Eu{sup 3+} and La{sup 3+} compounds.

OSTI ID:
21372575
Journal Information:
Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 4 Vol. 183; ISSN 0022-4596; ISSN JSSCBI
Country of Publication:
United States
Language:
English