Intramolecular [π4s + π4s] photocycloaddition of carbon- and nitrogen-bridged [3₂](1,4)naphthalenophanes

[3₂](1,4)Naphthalenophanes, bearing carbon-bridge chains (syn- and anti-NPs) and nitrogen-bridge chains (syn- and anti-ANPs), were synthesized, and their X-ray structures and photoreactions were investigated. The intramolecular separation distance between the naphthalene cores for ANPs was shorter than that for NPs, suggesting that intramolecular interactions between the naphthalene rings were more efficient for ANPs compared to NPs. Upon photoirradiation at 300 nm, anti-NP, syn-ANP and anti-ANP produced the corresponding intramolecular [π4s + π4s] cycloadducts, whereas syn-NP gave an unidentified complex product mixture. Quantum yields for the photo-consumption (Φ_PC) of NPs and ANPs were evaluated to quantitatively compare their photoreactivity. The Φ_PC values of ANPs were approximately two-fold higher than those of ANPs.Noteworthily, the Φ_PC value of syn-ANP was estimated to be unity. Based on these results we discuss the effects of the alignments of the naphthalene cores (antivs. syn) and the bridging elements (C-bridge vs. N-bridge) on the photoreaction efficiencies of [3₂](1,4)naphthalenophanes. Graphical abstract: (Figure presented.)