A novel example of double reactivity by either photochemical [2+2] or thermal additions of an ionic organic supramolecular assembly

An example of double reactivity in the solid state was achieved from a single binary array directed by charge-assisted hydrogen bonds assembled via mechanochemistry: [(HFu − )(Im + )] ( 1 ). The photochemical transformation of 1 occurs via a topotactic fashion with a quantitative yield followed by a second grinding-irradiation cycle. The recrystallisation of the photoproduct produces a novel hydrogen supramolecular isomer of [( rctt -H 2 Cbtc 2− )(Im + ) 2 ] ( 2 ). Another example of the regioselective and quantitative preparation of rtct -cyclobutane isomers was obtained from the controlled isomerisation of 2 under hydrothermal conditions. Upon heating, 1 produced an unexpected hydroamination product ( 3 ) in almost quantitative yield. The stereochemistry of products 2 and 3 was confirmed by X-ray single crystal diffraction analysis.