Based on the above concept, cyclophane-type dications 2 2+ with planar 3,6-dialkoxyxanthylium units were designed, with the expectation that the stacking of cationic units could be realized by effective interaction through three-carbon linkers. In addition, since reduction of 2 2+ efficiently decreases electrostatic repulsion between -conjugated units to make further proximity between them, the redox interconversion with the one-or two-electron reduced species could allow reversible control of the photophysical properties based on a change in the stacking environment (Figure ). Regarding the additional aryl group at the 9-position of xanthylium, 4-methoxyphenyl and 4-dimethylaminophenyl groups with different electron-donating properties were selected to investigate the influence of electronic properties. We also introduced a 5-(4-methoxyphenyl)-thienyl group, which is expected to stabilize radical cationic and biradical species based on the effective delocalization of a positive charge or an unpaired electron due to extension of the conjugated system. As shown in Scheme 1, cyclic diketone 7 was prepared by the reaction of 3,6-dihydroxyxanthen-9-one 4 with tosylated 2,2-diethyl-1,3-propanediol 5 in a stepwise manner. For the latter cyclic reaction, we adopted high dilution conditions (5 mM in DMF). The gem-diethyl-substituted linkers would contribute to the efficient formation (Thorpe-Ingold Effect ) of an intramolecular cyclic compound rather than linear oligomers, and the desired macrocyclic diketone 7 was isolated in 63% yield. When diketone 7 was reacted with the corresponding aryl lithium reagents, precursor diols 8a-8c were obtained in 70%, 54%, and 73% yields, respectively.