The syntheses and electrochemical and magnetochemical properties of (NBu(4)(II)) [Mn8O6Cl6(O(2)CPh)(7)(H2O)(2)]. xCH(2)Cl(2) (2 . xCH(2)Cl(2)) and [Mn9Na2O7(O(2)CPh)(15) (MeCN)(2)]. 3MeCN (3 . 3MeCN) are reported. Both complexes were prepared from reactions involving (NBu(4)(II))[Mn4O2(H2O)(O(2)CPh)(9)] (1). Complex 2 was obtained in 45-60% yield on treatment of complex 1 with 4 equiv of Me(3)SiCl in CH2Cl2. Complex 2 . 3/2CH(2)Cl(2) . 2H(2)O crystallizes in triclinic space group P (1) over bar with the following cell parameters at -169 degrees C : a 16.104(4) Angstrom, b= 21.501(6) Angstrom, c = 14.843(4) Angstrom, alpha = 94.24(1)degrees, beta = 105.96(1)degrees, gamma = 89.07(1)degrees, V = 4927.79 Angstrom(3), and Z = 2. The structure was refined by employing 10 108 unique reflections with F > 3.0 sigma(F) to give R = 0.0912 and R(w) = 0.0944. Complex 2 contains a [Mn8O6Cl4](8+) core (8Mn(III)) that may be conveniently described as resulting from the fusion of two [Mn4O2] butterfly units by sharing one "body" or "hinge" Mn. An eighth Mn-III ion is connected to the resultant [Mn7O4] unit by two additional bridging O2- ions.