A Rational Approach to Tetra‐Functional Photo‐Switches

α,ω‐Bis(1,8‐dichloroanthracen‐10‐yl)alkanes with (CH(2))(n)‐linker units (n=1–4) were synthesized starting from 1,8‐dichloroanthracen‐10(9H)‐one. This was transformed into anthracenes with allyl, bromomethyl and propargyl substituents in position 10; these were converted in various C−C‐bond formation reactions (plus hydrogenation), leading to two anthracene units flexibly linked by α,ω‐alkandiyl groups. 1,2‐Ethandiyl‐ and 1,3‐propandiyl‐linked derivatives were functionalized with ethynyl groups in positions 1, 8, 1’ and 8’, and these terminally functionalized by Me(3)Sn groups using Me(2)NSnMe(3). All linked bisanthracenes were subjected to UV light induced cyclomerization and a series of 9,10 : 9’,10’‐photo‐cyclomers were obtained. Their thermal cycloreversion and (repeated) switchability was demonstrated. 1,3‐Bis{1,8‐bis[(trimethylstannyl)ethynyl]anthracen‐10‐yl}propane served as model compound for photo‐switchable acceptor molecules and its open and closed forms were characterized by NMR and DOSY experiments.