Issue 33, 2022

Photophysical comparison of Zn(ii) phthalocyanaine tetrasulfonate and Zn(ii) tetrakis(4-sulfonatophenyl)porphyrin encapsulated within the Zn-polyhedral metal organic framework, HKUST-1(Zn)

Abstract

Porphyrins and phthalocyanines are ideal candidates for the development of photoactive porous metal organic frameworks (MOFs) due to their broad absorption spectra in the visible and near UV regions, high molar extinction coefficients and long triplet state lifetimes. An important factor in the development of porphyrin/phthalocyanine based MOFs is the extent to which the pore modulates the photophysical properties of the guest. Here, two structurally related guests, Zn(II)tetra(4-sulfonatophenyl)porphyrin (Zn4SP) and Zn(II)phthalocyanine tetrasulfonate (ZnPcS4) have been encapsulated within the pores of the MOF HKUST-1(Zn). Both the ZnPcS4@HKUST-1(Zn) and Zn4SP@HKUST-1(Zn) display bathochromic shifts in the Soret absorption band and steady state emission spectra as well as biphasic emissions lifetimes, relative to the chromophores in solution. These results are consistent with the pore modulating the excited state conformations of both chromophores. Interestingly, rotational control of the phenyl groups associated with Zn4SP@HKUST-1(Zn) appears to have a moderate impact on the photophysics.

Graphical abstract: Photophysical comparison of Zn(ii) phthalocyanaine tetrasulfonate and Zn(ii) tetrakis(4-sulfonatophenyl)porphyrin encapsulated within the Zn-polyhedral metal organic framework, HKUST-1(Zn)

Article information

Article type
Paper
Submitted
27 May 2022
Accepted
28 Jul 2022
First published
09 Aug 2022

Dalton Trans., 2022,51, 12729-12735

Photophysical comparison of Zn(II) phthalocyanaine tetrasulfonate and Zn(II) tetrakis(4-sulfonatophenyl)porphyrin encapsulated within the Zn-polyhedral metal organic framework, HKUST-1(Zn)

R. W. Larsen and L. Wojtas, Dalton Trans., 2022, 51, 12729 DOI: 10.1039/D2DT01667B

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