Adamantane as a Building Block in the Construction of Crown Ethers and Cryptands: Synthesis, Structure and Properties

Pripravljeni su novi adamantanski i oksaadamantanski krunasti eteri i kriptandi te je ispitivana njihova sposobnost kompleksiranja s metalnim kationima. U tom tipu spojeva adamantanska molekula služi kao kruti dio koji smanjuje konformacijsku pokretljivost cijele molekule, a utječe i na dimenziju i oblik šupljine makrocikličkog prstena u odnosu na osnovni nesupstituirani sustav. Rezultati eksperimenata ekstrakcije te rezultati molekulskog modeliranja odgovarajućih K+ kompleksa pokazali su da preorganiziranost molekule-domaćina ima znatan utjecaj na sposobnost molekule za interakciju s metalnim ionima i stvaranje kompleksa.Several new adamantane- and oxaadamantane-containing crown ethers and cryptands have been synthesized, and their ability to complex metal cations has been studied. In molecules of this type, the adamantane moiety functions as a rigid spacer that lowers the conformational mobility of the host molecule and also affects the size and shape of the host cavity relative to the corresponding parent non-substituted system. The results of the extraction experiments combined with the molecular modeling studies of the corresponding K+complexes showed, that preorganization in given host-molecules exerts a dramatic influence upon that molecule's ability to interact effectively with guest metal ions to form corresponding host-guest complex