Synthesis, characterization and oscillator-vibrated near-infrared (NIR) luminescence of two pseudo-polymorphic [Yb4((OH)2-Salophen)4] complexes

Abstract

Through the self-assembly of the (OH)2-Salophen H4L (H4L=N,N'-bis(3-hydroxylsalicylidene)benzene-1,2-diamine) with LnCl3·6H2O or Ln(NO3)3·6H2O (Ln=La, Yb or Gd) in different solvent systems MeCN-EtOH and MeCN-DMF, the mixed (L)(4-) and (H2L)(2-) coordination modes induce the formation of anion-independent while pseudo-polymorphic homoleptic linear tetranuclear complexes [Ln4(H2L)2(L)2(EtOH)2] (Ln=La, 1; Ln=Yb, 2 or Ln=Gd, 3) and [Ln4(H2L)2(L)2(DMF)2] (Ln=La, 4; Ln=Yb, 5 or Ln=Gd, 6), respectively. The result of their photophysical properties shows the characteristic NIR luminescence for both Yb(3+)-based complexes 2 and 5 with emissive lifetimes in microsecond ranges, while the difference of nearby and/or distant oscillator-based (OH and/or CH) vibrations from two coordinated EtOH or DMF molecules within the inner coordination spheres of Yb(3+) ions in the two complexes has a decisive effect on their NIR luminescent properties.

Keywords: Oscillator-vibrated NIR luminescence; Pseudo-polymorphism; Tetranuclear [Ln(4)((OH)(2)-Salophen)(4)]-arrayed complexes.