Elimination of Dimer Formation in In^IIIPorphyrin-Based Anion-Selective Membranes by Covalent Attachment of the Ionophore

The spontaneous hydroxy-bridged dimer formation of metalloporphyrins in ion-selective membranes gives rise to a short sensor lifetime (typically days), triggered by solubility problems, the occurrence of a super-Nernstian response slope, and a pH cross response. This dimer formation is eliminated here by covalent attachment of the ionophore to the polymer matrix. Specifically, two different indium(III)porphyrins containing polymerizable groups, the chloride-selective chloro(3-[18-(3-acryloyloxypropyl)-7,12-bis(1-methoxyethyl)-3,8,13,17-tetramethylporphyrin-2-yl]propyl ester)indium(III) and the nitrite-selective Chloro(5-(4-acryloyloxyphenyl)-10,15,20-triphenylporphyrinato)indium(III), were synthesized and copolymerized with methyl methacrylate and decyl methacrylate. The covalent attachment of the ionophore to the polymer matrix indeed prevents the metalloporphyrin from forming dimeric species, as confirmed by UV/visible spectroscopy. The ion-selective membranes with grafted indium porphyrin showed Nernstian response slopes to chloride, nitrite, perchlorate, and thiocyanate anions, with a selectivity comparable to membranes with freely dissolved or underivatized metalloporphyrin. The membranes containing grafted ionophores showed a lifetime of at least two months, apparently since crystallization of the poorly soluble dimeric species may no longer occur. This is one of the first examples where the covalent attachment of an ionophore drastically improves on a number of important sensor characteristics.