The solvothermal synthesis of vanadyl phosphonates has been studied under d
ifferent conditions. Starting from dichlorovanadate, M[(VO2Cl2)-O-V] (M = P
Ph4, MePPh3), or decavanadate and phosphonic acids, RPO3H2 (R = Me, tBu, Ph
), the formation of oxovanadium clusters under the directing influence of t
emplates as well as of different solvents has been investigated. It is also
shown that the cation M influences the formed oxovanadium structures as we
ll as the rests in the phosphonic acids because of their different steric b
ehaviour.