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

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