Diorganodiphosphates (DPP2-), triorganodiphosphates (TPP-), a diorganotriphosphate (DPPP3-), and a triorganomethylenediphosphonate (TPCP-) were reacted with zinc perchlorate to form the complex compounds Zn(DPP), Zn(TPP)(2), Zn-3(DPPP)(2), and Zn(TPCP)(2). Spectroscopic investigations and the solubility properties allow to assign Zn(DPP) and Zn-3(DPPP)(2) as coordination polymers, while Zn(TPP)(2) and Zn(TPCP)(2) are molecular complexes. (C) 2000 Elsevier Science S.A. All rights reserved.