Tri- [Pt2Tl] 3- and Polynuclear Chain Complexes [Pt-Tl] ¥- Based on Non-bridged PtII-Tl Bonds : Solid State and Frozen Solution Photophysical Properties

  1. Falvello, L.R. 2
  2. Forniés, J. 2
  3. Garde, R. 2
  4. García, A. 1
  5. Lalinde, E. 1
  6. Moreno, M.T. 1
  7. Steiner, A. 3
  8. Tomás, M. 2
  9. Usón, I. 24
  1. 1 Universidad de La Rioja

    Universidad de La Rioja

    Logroño, España


  2. 2 Instituto de Nanociencia y Materiales de Aragón

    Instituto de Nanociencia y Materiales de Aragón

    Zaragoza, España


  3. 3 University of Liverpool

    University of Liverpool

    Liverpool, Reino Unido


  4. 4 Institució Catalana de Recerca i Estudis Avançats

    Institució Catalana de Recerca i Estudis Avançats

    Barcelona, España


Inorganic Chemistry

ISSN: 0020-1669

Año de publicación: 2006

Volumen: 45

Número: 6

Páginas: 2543-2552

Tipo: Artículo

DOI: 10.1021/IC051818U SCOPUS: 2-s2.0-33645510653 WoS: WOS:000236119700033 GOOGLE SCHOLAR


Treatment of (NBu4)2[PtR4] (R = C 6F5) with 1 or 0.5 equiv of TlNO3 in EtOH/H2O produces colorless crystals of trinuclear complex (NBu 4)3[Tl{PtR4}2], 1, in which the Tl+ center is complexed by two [PtR4]2- fragments (Pt-Tl = 2.9777(4) and 3.0434(4) Å). The expected mixed complex with a Pt/Tl composition of 1:1, 2, is generated as an orange microcrystalline solid by treating [PtR4]2- with a large excess of TlNO3 (∼8 equiv). Crystallographic analysis of 2 reveals the formation of a novel one-dimensional (1D) heterometallic linear chain (NBu 4)∞[Tl{PtR4}]∞, 2, formed by alternating a [PtR4]2- fragment and a Tl + center with a uniform Pt-Tl bond separation along the chain of 3.0321(2) Å. Surprisingly, treatment of (NBu4) 2[PtR4] with 1 equiv of TlPF6 in EtOH yields pale greenish-yellow needles of an unusual adduct, 2·{(NBu 4)(PF6)}∞ (3), which was found to form a similar extended linear chain, {TlPtR4}∞, constructed by two alternating Pt-Tl separations, a shorter (3.1028(6) Å) one and a longer (3.2306(6) Å) one. The solid state and solution photophysical properties have been examined. While complex 1 shows a high-energy MM′CT blue phosphorescence (450 nm), the extended chain in 2 exhibits a lower-energy emission (582 nm) than that in adduct 3 (505 nm). For products 2 and 3, interesting luminescence thermochromism is observed in frozen solutions. The emissions are found to be strongly dependent on the solvent, concentration, and excitation wavelength. © 2006 American Chemical Society.