First Examples of Near‐Infrared Luminescent Poly(methyl methacrylate)‐Supported Metallopolymers Based on Zn 2 Ln‐Arrayed Schiff Base Complexes

The first examples of Wolf Type II Zn 2 Ln‐containing metallopolymers poly{MMA‐ co ‐[Zn 2 ( L ) 2 (4‐vp) 2 Ln(NO 3 ) 3 ]} (Ln = La, Nd, Yb, Er, Gd; H 2 L = N , N′ ‐bis(salicylidene)ethylene‐1,2‐diamine; 4‐vp = 4‐vinylpyridine; MMA = methyl methacrylate) are obtained from the controlled copolymerization of heterotrinuclear Zn 2 Ln‐arrayed complexes [Zn 2 ( L ) 2 (4‐vp) 2 Ln(NO 3 ) 3 ] (Ln = La, 1 ; Ln = Nd, 2 ; Ln = Yb, 3 ; Ln = Er, 4 ; Ln = Gd, 5 ) with MMA. The strong and characteristic near‐infrared (NIR) luminescent Ln 3+ ‐centered emission for each of the PMMA‐supported poly{MMA‐ co ‐[Zn 2 ( L ) 2 (4‐vp) 2 Ln(NO 3 ) 3 ]} (Ln = Nd, Yb, Er) hybrid materials is retained with somewhat higher intrinsic quantum yields than those of the respective Zn 2 Ln‐arrayed complex. Especially for poly(MMA‐ co ‐ 3 ), which has more efficient sensitization from both ligand‐centered singlet ( 1 LC) and triplet ( 3 LC) states of the chromophores, the concentration self‐quenching of Yb 3+ ‐based NIR luminescence could be effectively prevented.