Nickel(ii) monobenzoporphyrins and chlorins: synthesis, electrochemistry and anion sensing properties

Abstract

A series of nickel(II) monobenzochlorins (MBCs) and monobenzoporphyrins (MBPs) containing β-appended or meso,β-fused indanedione (IND) or malononitrile (MN) groups were synthesized and characterized for their physicochemical, electrochemical and anion sensing properties. Each investigated compound contained four meso-phenyl rings and a single β,β′-fused 4,5-di(methoxycarbonyl)benzene ring, with the chlorins represented as NiMBC(Y)₂(R)₄ and the porphyrins as NiMBP(Y^F)₂, where Y is an indanedione (IND) or malononitrile (MN) group, R = H or Br and Y^F is a meso,β-fused IND or MN substituent. One of the investigated compounds, NiMBP(IND)₂, was structurally characterized and shown to possess a ruffled macrocyclic conformation. The monobenzochlorins, NiMBC(IND)₂, NiMBC(IND)₂Br₄ and NiMBC(MN)₂, reversibly respond to basic anions such as CN⁻, F⁻, OAc⁻ and H₂PO₄⁻ through a visible color change assigned to the deprotonation of the vicinal proton on the appended IND or MN substituents. The malononitrile-fused Ni^II monobenzoporphyrin, NiMBP(MN)₂, exhibited a selective but irreversible visual detection of cyanide ions (LOD = 2.23 ppm). This reaction afforded a tri-fused π-extended monobenzoporphyrin product represented as NiMBP(VCN)₂ (where VCN = meso,β-fused vinyl cyanide) in non-aqueous media and proceeded via anion induced electron transfer (AIET). The in situ generated π-extended porphyrin was also isolated and characterized as to its physicochemical and electrochemical properties and found to possess a narrow electrochemical HOMO–LUMO gap of 1.46 V along with a near-IR (NIR) absorption band located at 861 nm.