Publication

Abstract : A series of Co(II), Ni(II) and Cu(II) derivatives of a variety of porphyrins with tolyl (H2TxTP) and naphthyl (H2NxTP) moieties as meso-substituents are synthesised and characterised. {H2TxTP} has the tolyl functions bonded to meso-carbons at the o-, m- or p-positions of the tolyl moieties while {H2NxTP} has naphthyl groups bonded through their α- or β-positions. Their octabromo derivatives (MTxOBP and MNxOBP) were also synthesised by electrophilic substitution at the β-pyrrole positions. Optical spectra showed that the Q bands remain almost unaltered for both tolyl and naphthyl derivatives of the nonbrominated porphyrins while the B bands of their naphthyl derivatives are seen to be more red-shifted than their tolyl analogues. Even though a similar trend based on the meso-substituents is observed among all {MTxOBP} and {MNxOBP} derivatives, a substantial red-shift is seen for all the bromoderivatives compared to their nonbrominated species {MTxTP} and MNxTP. The energy difference Δ ν ¯ associated with this red-shift of the Soret band is seen to be in the range 1700–2050 cm−1 for Co(II) and Ni(II) derivatives, the naphthyl derivatives always having higher values. Energy level reordering due to electron-withdrawing Br-substituents, distortion bringing about nonplanarity in the π-framework resulting in HOMO–LUMO level changes and the mesomeric effect due to meso-aryl moieties can be considered to be the reasons for the observed spectral changes. The {EPR} spectra of the Cu(II) derivatives of bromoporphyrins have lower A ∥ Cu and A ⊥ Cu hyperfine values compared to their nonbrominated analogues, indicating enhanced delocalisation of electron spin to the octabromoporphyrinato moiety. An enhanced Cu–N σ-covalency is seen in the Cu(II)–bromoporphyrins, as evident from their lower α2 values.