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Unique homoleptic cyclic tetranuclear Ln(4)(Salen)(4) complexes [Ln(4)(L)(2)(HL)(2)(μ(3)-OH)(2)Cl(2)]·2Cl (Ln = Nd, 1; Ln = Yb, 2; Ln = Er, 3; Ln = Gd, 4) or Ln(4)(Salen)(2) complexes [Ln(4)(L)(2)(μ(3)-OH)(2)(OAc)(6)] (Ln = Nd, 5; Ln = Yb, 6; Ln = Er, 7; Ln = Gd, 8) have been self-assembled from the reaction of the hexadentate Salen-type Schiff-base ligand H(2)L with LnCl(3)·6H(2)O or Ln(OAc)(6)·6H(2)O (Ln = Nd, Yb, Er, or Gd), respectively (H(2)L: N,N'-bis(salicylidene)cyclohexane-1,2-diamine). The result of their photophysical properties shows that the strong and characteristic NIR luminescence for complexes 1-2 and 5-6 with emissive lifetimes in microsecond ranges are observed, and the sensitization arises from the excited state (both (1)LC and (3)LC) of the hexadentate Salen-type Schiff-base ligand with the flexible linker. Temperature dependence (1.8-300 K) magnetic susceptibility studies of the eight complexes suggest the presence of an antiferromagnetic interaction between the Ln(3+) ions.

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