PbnI4n+2(2n+2)− (n = 3, 5) ribbons, which can be regarded as dimensional reductions of 2D perovskite layers, are stabilized by diprotonated cystamine cations in (NH3(CH2)2SS(CH2)2NH3)4Pb3I14,I2 (1) and (NH3(CH2)2SS(CH2)2NH3)6Pb5I22·4H2O (2). Both 1 and 2 have interesting structural characteristics; it is unprecedented that the ribbons are linked via I2 molecules incorporated in the lattice of 1, while tetrameric water clusters are trapped in the structure of 2. 2 undergoes a (reversible) water desorption process at 310 K leading to (NH3(CH2)2SS(CH2)2NH3)6Pb5I22·2H2O (3). The electrical behavior of 2 and 3 has been investigated in the ranges 293–310 K and 310–358 K respectively. Above 310 K, the electronic contribution remains constant while the ionic transference number tends towards unity showing almost pure ionic transport at 360 K (6 × 10−7 S cm−1 at 330 K) originating probably from the migration of protons through the hydrogen bonds connecting the water molecules to the cystamine counter cations.
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