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The crystal structure of the palladium(II) complex containing eight alkyl chains with five carbon atoms was unequivocally elucidated by means of single\u2010crystal XRD studies. The thermal behaviour of the new compounds was studied by polarised light optical microscopy and differential scanning calorimetry. Porphyrins with eight terminal alkyl chains containing five and eight carbon atoms, and the corresponding palladium(II) complexes, behave as liquid\u2010crystalline materials, exhibiting lamellar columnar mesophases at temperatures above 80\u2009\u00b0C. 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