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Complexes of aryl-substituted porphyrins and naphthalenediimide (NDI): investigations by synchrotron X-ray diffraction and NMR spectroscopy

Lookup NU author(s): Professor William Clegg, Dr Jeremy Lowe

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Abstract

New donor-acceptor hybrids of Zn(II)-metallated 5,15-diaryl porphyrins have been designed and synthesised via the porphyrin interactions with an electron acceptor molecule, di-n-hexyl N-substituted 1,2,4,8-naphthalenetetracarboxylic diimide (NDI). Binding interactions within these supramolecular complexes were investigated in the solid state by synchrotron X-ray diffraction and probed in solution by H-1 NMR spectroscopy. The systematic modulation of the porphyrin pi-density was achieved, for the first time as multiple methoxy and fluorine groups were introduced as substituents to the 5,15-diaryls of the porphyrin. For these, the variation of the porphyrin-NDI binding strengths determined by H-1 NMR titrations was shown, using the Swain's type dual parameter approach, to be closely linked with the peripheral substitution pattern of the diaryl porphyrins validated by crystallography. The new 1 : 1 donor-acceptor complexes formed display characteristic features of the aromatic-stacked systems, i.e. the parallel arrangement and short interplanar separation between the substituted porphyrin and NDI. Synthetic modification of electron-density on the porphyrin surface by introducing substituents at peripheral sites of functionalised porphyrins represent a general solution towards electronically tunable aromatic surfaces: an understanding of their solution and solid state behaviour will significantly improve the rational design of new functional donor-acceptor supramolecular materials with potential applications ranging from new energy materials to dye-sensitised solar cells, photovoltaics and future drug delivery devices.

Publication metadata

Author(s): Tong LH, Pengo P, Clegg W, Lowe JP, Raithby PR, Sanders JKM, Pascu SI

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2011

Volume: 40

Issue: 41

Pages: 10833-10842

Print publication date: 22/07/2011

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/c1dt10880h

DOI: 10.1039/c1dt10880h

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