Conformational Switching of A Nano‐Size Urea‐bridged Zn(II)Porphyrin Dimer by External Stimuli

For the first time, explicit stabilization of all the three conformers, viz. (cis,cis), (cis,trans) and (trans,trans), of a ‘nano‐sized’ highly‐flexible urea‐bridged Zn(II)porphyrin dimer have been achieved via careful manipulations of external stimuli such as solvent dielectrics, temperature, anionic interactions, axial ligation and surface‐induced stabilization. The conformers differ widely in their structures, chemical and photophysical properties and thus have vast potential applicability. X‐ray structural characterizations have been reported for the (cis,cis) and (cis,trans)‐conformers. While (cis,cis) conformer stabilized exclusively in dichloromethane, more polar solvents resulted in the stabilization of (cis,trans) and (trans,trans)‐conformers. Low temperature promotes the stabilization of (cis,trans)‐conformer while rise in temperature facilitates flipping to the (cis,cis) one. Significantly, exclusive stabilization of the (trans,trans)‐isomer has been illustrated using acetate anion which facilitates H‐bonding with the two amide linkages of the urea spacer. Remarkably, HOPG surface facilitates stabilization of the energetically challenging (trans,trans)‐conformer via CH···p and p···p interactions with the solid surface to the porphyrinic cores. DFT calculations demonstrate that the relative stability of the conformers can be modulated upon slight external perturbations as also observed in the experiment. Several factors contributing towards the conformational landscape for the highly flexible urea‐bridged porphyrin dimers have been mapped.