Reactions between [Nb₆Cl₁₂(CN)₆]^4- and [Mn(salen)]⁺ led to formation of [Mn₂(salen)₂(H₂O)₂][(Mn(salen))₂(Nb₆Cl₁₂(CN)₆)] (1). 1 is a 2D anionic 4,4-net built of [Nb₆Cl₁₂(CN)₆]^4- and [Mn(salen)]⁺ with dimers [Mn₂(salen)₂(H₂O)₂]²⁺ as cation. Unusual solvent-mediated structural transformations have been observed when 1 is exposed to solutions of different cations. Thus, in contact with methanol solution of [Me₄N]⁺ 1 undergoes solvent-mediated ion-exchange reactions to form (2). In contact with methanol solution of (Et₃BzN)⁺ a mixture of [Et₃BzN]₂[{(Mn(salen)(MeOH))₂(Nb₆Cl₁₂(CN)₆)}] (3) and [Et₃BzN]₂[(Mn(salen))₂(Nb₆Cl₁₂(CN)₆)] (4)  are formed as crystals. 3 features same 2D anionic 4,4-net as that observed for 1 and 2 but different layer stacking and interlayer spacing. 4 consists of heterotrimeric supramolecular anions built of (Nb₆Cl₁₂(CN)₆)^4- linked to two [(Mn(salen)(H₂O)]⁺. When 1 is left in methanol solution of Li⁺ (or Na⁺, K⁺, (Bu₄N)⁺, PPh₄⁺), or in neat solvents (MeOH or MeOH + H₂O or MeCN), a heteropentamer built of (Nb₆Cl₁₂(CN)₆)^4- linked to four [(Mn(salen)(MeOH)]⁺ was obtained: [{(Mn(salen)(MeOH))₄(Nb₆Cl₁₂(CN)₆)}] (5).