This paper presents the synthesis of several new Schiff-base type expa
nded porphyrins. A dimeric, tetraazacyclodotetradecane-linked texaphyr
in system has been prepared. It, as its gadolinium(III) adduct, displa
ys a relaxivity in aqueous solution that is roughly 5 times higher tha
n the benchmark texaphyrin monomer currently undergoing human clinical
trials as a potential MRT enhancing and X-ray radiation sensitizing d
rug. Polymeric gadolinium(III) texaphyrin species, derived from poly-l
-lysine and a glycosylated poly-l-lysine, have also been prepared; the
y too display greatly enhanced relaxivities. In work along different l
ines, the synthesis of an ''expanded'' texaphyrin has been effected an
d the construction of two ''three dimensional'' texaphyrin-inspired ta
rgets accomplished. These latter define a new class of pyrrolic crypta
nds.