Solid-state supramolecular chemistry of zinc tetraphenylporphyrin and zinc phthalocyanine with bis(pyridyl) ligands

Three new Z-shaped supramolecular complexes (C44H28N4Zn)2·(C14H14N4O2)·(C6H5Cl)4 (1), (C44H28N4Zn)2·(C14H14N4O2)·(CH2ClCH2Cl)2·(H2O)4 (2), and (C32H16N8Zn)2·(C14H14N4O2)·(DMF)4 (3) have been prepared by Zinc tetraphenylporphyrin(ZnTPP) and/or Zinc phthalocyanine(ZnPc) with bis(pyridyl) ligands (pyCH2NHCOCONHCH2py, py = 3 or 4-pyridyl), which are ditopic ‘Z’ type ligands. In all of the complexes the central Zn atom is equatorially coordinated by four isoindole N atoms of Pc or TPP macrocycle and axially by N atom of bis(pyridyl) ligands. The interaction of the central Zn atom of ZnTPP and ZnPc with the axial N atom of bis(pyridyl) molecule leads to a deviation of Zn from the basal plane towards the bis(pyridyl) ligands by 0.2 Å in complexes 1–3. The electronic absorption spectra and fluorescence spectra reveal that all of the three supramolecular complexes have a blue-shift and display strong fluorescence.