Synthese multivalenter Organophosphonsäuren und - silanole. Neue Bausteine in der supramolekularen Chemie.

Abstract

We present the Synthesis of new multifunctional organosilanols for their use in supramolecular chemistry and -phosphonic acids as linkers in metal phosphonates. The tri- and tetrasilanols benzene-1,3,5-tri-p-phenyl(hydroxydiisopropylsilane) (4), benzene-1,3,5-tri-p-biphenyl(hydroxydiisopropylsilane) (8) and tetrakis[(4-(hydroxydiisopropylsilyl)biphenyl)]silane (16) were synthesized. The supramolecular structures have been studied using the TOPOS program. For the synthesis of multivalent phosphonic acids a new synthetic route, the suzuki-coupling of 4-(Dimethoxy¬phosphoryl)phenylboronic acid to numerous aryl bromides, was established. In addition, the potentially photo switchable trans(E)-azobenzenebis(4-phosphonic acid) (31) was prepared. The luminescent phosphonic acids, anthracene-9,10-bisphosphonic acid (36), anthracen-9,10-bis(4'-phenylphosphonic acid) (38), pyrene-1,3,6,8-tetrakisphosphonic acid (40) and pyrene-1,3,6,8-tetrakis(4'-phenyl¬phosphonic acid) (42), have been synthesized and investigated by fluorescence spectroscopy. Furthermore the synthesis of the tetrahedral phosphonic acids, tetraphenylsilane-tetrakis(4-phosphonic acid) (44) and tetrabiphenylsilane-tetrakis(4-phos¬phonic acid) (47) is described. Two metal phosphonates are obtained from 44 with copper and zinc, which have been characterized by X-ray structure analysis.