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Protonation of trans-1,2-bis(4-pyridyl)ethylene (4,4′-bpe) with dilute sulfuric acid (33 %) afforded a protonated adduct [{4,4′-bpe⋅2 H+}2{HSO4}−2{SO4}−2{H2O}2] ( 1). The neighboring olefinic bond in 1 is in a suitable range (3.931-4.064 Å) to undergo a photochemical [2+2] cycloaddition reaction. Upon irradiation with UV light (365 nm), 1 undergoes a molecular sliding involving the 4,4′-bpe⋅2 H+ units, affording 2, stabilized through OSO4⋅⋅⋅π interactions. Heating 1 to 50° C leads to a 3D hydrogen-bonded organic framework (HOF) ( 3). This process occurs through thermal dissociation of the bisulfate anion. Diffusion of iodine through the crystal lattice of 1 and 3 enables the reduction of sulfate to bisulfate, affording a 1D hydrogen-bonded chain ( 4). Solid-state 13C CPMAS NMR, IR, DSC, and powder XRD studies further support stimuli-responsive structural tuning through crystal-to-crystal transformation. All these conversions occur with significant translational and rotational movements along with a series of bond-breaking and bond-forming processes. [ABSTRACT FROM AUTHOR]