Earlier studies of DADQ derivatives in our laboratory, and their prominent f luorescence response variation between the A and C states is a pertinent case in this context. In particular, reversible phase change induced by thermal stimuli was realized in select alkoxyalkyl DADQ derivatives, leading to the f irs t example of f unctional molecular phase change materials. An important observation in this study was that, unlike the DADQs reported earlier which had melting/decomposition temperatures typically > 250 °C, the ROR′-DADQs melt without decomposition typically at < 200 °C; this allowed the creation of the A phase by standard techniques like melt-quench or laser irradiation, and the realization of reversible transition to the C phase under suitable thermal stimuli. In a broad sense, the uniqueness of ROR′-DADQs may stem f rom the combination of the conf ormational f lexibility of the appropriate substituent groups coupled with the strong electrostatic interactions of the zwitterionic aromatic core unit. We visualized that, at a molecular level the role of the R and R′ links would be crucial in realizing the delicate balance. This led us to explore two series of ROR′-DADQs with a systematic progression of the alkoxyalkyl chains; the ease of preparing them through simple single step synthesis under mild conditions, and their amenability to complete structural characterization were added attractions. We describe below the insightf ul structuref unction correlations unraveled through the spectrosco pic evaluation of the f luorescence variation accompanying the A-C transitions and their temporal evolution, monitoring of the thermal behavior of the molecular solids, and detailed crystallographic investigations.