Octacalcium phosphate with incorporated terephthalate ion derivatives: novel guest molecules and unique fluorescence properties

Abstract

Octacalcium phosphate (OCP), an inorganic compound with a layered structure that can incorporate various carboxylic acids, exhibits fluorescence when aromatic carboxylate ions are present in the interlayers. However, the incorporation of carboxylate ions into OCP involves molecular selectivity, and the synthesis of novel OCP materials with incorporated terephthalate ion derivatives is particularly challenging. In this study, we incorporated 4-(carboxymethyl)benzoate and 1,4-phenylenediacetate ions into OCP for the first time and investigated the resulting fluorescence properties. The relationship between the (100) interplanar spacing and size of the incorporated dicarboxylate ions revealed that 4-(carboxymethyl)benzoate ions have a relaxed structure in the OCP interlayers, whereas the structure of the 1,4-phenylenediacetate ions is elongated by approximately 10% relative to that of the stable conformation. OCP with incorporated 1,4-phenylenediacetate ions showed blue fluorescence at 286 nm under 254 nm excitation. In contrast, distinct from previously reported fluorescent OCPs, OCP with incorporated 4-(carboxymethyl)benzoate ions exhibited two-colour fluorescence, with pink emission under 254 nm excitation and blue emission under 312 and 365 nm excitation. This OCP material exhibiting fluorescence at two wavelengths in the visible-light range offers new possibilities for practical applications. In particular, these unique fluorescence characteristics combined with the excellent biological properties of OCP can be exploited to develop novel biofriendly fluorescent probes. These findings contribute to an improved understanding of fundamental calcium phosphate chemistry and should encourage further research on functional OCP materials.