Unique quadridentate salen type triple-decker dinuclear sandwich ytterbium complex [Yb₂L₃(CH₃OH)]·0.5H₂O (1) and triple-decker trinuclear sandwich ytterbium complex [Yb₃L₃(CH₃OH)₂(NO₃)₃]·CH₃OH·5H₂O (2) are isolated from the reactions of Yb(OAc)₃·4H₂O and Yb(NO₃)₃·6H₂O with H₂L, respectively (H₂L = N,N′-bis(salicylidene)-1,2-(phenylene-diamine)). Complex 2 could be harvested from the addition of complex 1 and Yb(NO₃)₃·6H₂O. Near infrared (NIR) lanthanide luminescence and the lifetime of complexes 1 and 2 are conducted and described.