Reversible open–closed conformational switching of nano-size metalloporphyrin dimers triggered by light and temperature

Shah, Syed Jehanger; Singh, Ajitesh; Goswami, Debabrata; Ishida, Masatoshi; Rath, Sankar Prasad

doi:10.1039/d4dt00223g

Dalton Trans.

2024

DOI: 10.1039/d4dt00223g

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Reversible open–closed conformational switching of nano-size metalloporphyrin dimers triggered by light and temperature

Syed Jehanger Shah,

Ajitesh Singh,

Debabrata Goswami

et al.

Abstract: The current work demonstrates the reversible control of substantial molecular motion in 'nano-sized' molecules, where two structural isomers can 'open' and 'close' their cavities using light or heat. The isomers...

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

Saha,

Pal,

Malik

et al. 2024

Chemistry A European J

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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⋅⋅⋅π and π⋅⋅⋅π 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.

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

Saha,

Pal,

Malik

et al. 2024

Chemistry A European J

View full text Add to dashboard Cite

show abstract

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Reversible open–closed conformational switching of nano-size metalloporphyrin dimers triggered by light and temperature

Abstract: The current work demonstrates the reversible control of substantial molecular motion in 'nano-sized' molecules, where two structural isomers can 'open' and 'close' their cavities using light or heat. The isomers...

Cited by 1 publication

References 85 publications

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

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

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