TY - JOUR
T1 - A soft on/off switch based on the electrochemically reversible H-J interconversion of a floating porphyrin membrane
AU - Molina-Osorio, Andrés F.
AU - Yamamoto, Sho
AU - Robayo-Molina, Iván
AU - Gamero-Quijano, Alonso
AU - Nagatani, Hirohisa
AU - Scanlon, Micheál D.
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2021.
PY - 2021/8/14
Y1 - 2021/8/14
N2 - Soft molecular assemblies that respond reversibly to external stimuli are attractive materials as on/off switches, in optoelectronic, memory and sensor technologies. In this Edge Article, we present the reversible structural rearrangement of a soft porphyrin membrane under an electrical potential stimulus in the absence of solid-state architectures. The free-floating porphyrin membrane lies at the interface between immiscible aqueous and organic electrolyte solutions and is formed through interfacial self-assembly of zinc(ii)meso-tetrakis(4-carboxyphenyl)porphyrins (ZnPor). A potential difference between the two immiscible electrolyte solutions induces the intercalation of bis(triphenylphosphoranylidene)ammonium cations from the organic electrolyte that exchange with protons in the porphyrin membrane.In situUV/vis absorbance spectroscopy shows that this ionic intercalation and exchange induces a structural interconversion of the individual porphyrin molecules in the membrane from an H- to a J-type molecular configuration. These structural rearrangements are reversible over 30 potential cycles.In situpolarisation-modulation fluorescence spectroscopy further provides clear evidence of structural interconversion of the porphyrin membrane, as intercalation of the organic electrolyte cations significantly affects the latter's emissive properties. By adjusting the pH of the aqueous phase, additional control of the electrochemically reversible structural interconversion can be achieved, with total suppression at pH 3.
AB - Soft molecular assemblies that respond reversibly to external stimuli are attractive materials as on/off switches, in optoelectronic, memory and sensor technologies. In this Edge Article, we present the reversible structural rearrangement of a soft porphyrin membrane under an electrical potential stimulus in the absence of solid-state architectures. The free-floating porphyrin membrane lies at the interface between immiscible aqueous and organic electrolyte solutions and is formed through interfacial self-assembly of zinc(ii)meso-tetrakis(4-carboxyphenyl)porphyrins (ZnPor). A potential difference between the two immiscible electrolyte solutions induces the intercalation of bis(triphenylphosphoranylidene)ammonium cations from the organic electrolyte that exchange with protons in the porphyrin membrane.In situUV/vis absorbance spectroscopy shows that this ionic intercalation and exchange induces a structural interconversion of the individual porphyrin molecules in the membrane from an H- to a J-type molecular configuration. These structural rearrangements are reversible over 30 potential cycles.In situpolarisation-modulation fluorescence spectroscopy further provides clear evidence of structural interconversion of the porphyrin membrane, as intercalation of the organic electrolyte cations significantly affects the latter's emissive properties. By adjusting the pH of the aqueous phase, additional control of the electrochemically reversible structural interconversion can be achieved, with total suppression at pH 3.
UR - http://www.scopus.com/inward/record.url?scp=85112630060&partnerID=8YFLogxK
U2 - 10.1039/d0sc05786j
DO - 10.1039/d0sc05786j
M3 - Article
AN - SCOPUS:85112630060
SN - 2041-6520
VL - 12
SP - 10227
EP - 10232
JO - Chemical Science
JF - Chemical Science
IS - 30
ER -