A family of four isostructural complexes with a V-shaped pentanuclear [Zn(2)Ln(3)] core of general formula [Zn(2)Ln(3)(m-salen)(3)(N-3)(5)center dot(OH)(2)] [Ln(III) = Tb-III (1), Eu-III (2), Ho-III (3), Dy-III (4); m-salen = N,N-ethylenebis(3-methoxysalicylideneamine)] were isolated and structurally characterized. The fluorescence and magnetic measurements of the four compounds were investigated. Complex 1 exhibits strong fluorescence properties, while single-molecule-magnet behavior is seen in complex 4.