Twogenuine supramolecular isomers [Co(1,4-NDC)(5,5'-dmbpy)]n(1αand 1β) and compound {[Co(1,4-NDC)(5,5'-dmbpy)(H2O)2]2}n(2) (1,4-NDCH2= 1,4-naphthalenedicarboxylic acid, 5,5'-dmbpy= 5,5'-dimethyl-2,2'-dipyridyl) have been synthesizedunder conventional hydro(solvo)thermal reactions. The highly crystallinesingle-phases of 1βand 2with a well-definedmorphology could also be quickly prepared through microwave-assistedsyntheses within 5 min. Compared with 2, which possessesa one-dimensional (1D) single-chain-like structure, 1αand 1βfeature the structures of 1D ladder-likechain and two-dimensional (2D) layer, respectively, constructed fromthe ring-like [Co2(OOCR)2] dimeric units interlinkedby the 1,4-NDC ligands. The drastic structural transformation from 1αto 2, as well as the interconversionbetween 1βand 2, was observed, whichinvolved the reversible destruction and reconstruction of the Co2(OOCR)2unit during the transformation and wasassociated with remarkable changes in magnetic properties. Remarkably, microwave heating as an external driving force was adopted to achievestructure transformation from 2to 1βwithin 5 min. This work demonstrates that the microwave techniquecan be used as a quick and efficient synthetic method to investigatethe structural conversion between compounds and further bring aboutproperty modulation. [ABSTRACT FROM AUTHOR]