Encapsulation of Phosphorescent Pt(II) Complexes in Zn-Based Metal–Organic Frameworks toward Oxygen-Sensing Porous Materials

Abstract

In this work, we synthesized two tailored phosphorescent Pt(II) complexes bearing a cyclometalating tridentate thiazole-based C^N*N pincer luminophore (<b>L</b>) and exchangeable chlorido (<b>[PtCl(L)]</b>) or cyanido (<b>[PtCN(L)]</b>) coligands. While both complexes showed photoluminescence from metal-perturbed ligand-centered triplet states (³MP-LC), <b>[PtCN(L)]</b> reached the highest phosphorescence quantum yields and displayed a significant sensitivity toward quenching by ³O₂. We encapsulated them into two Zn-based metal-organic frameworks, namely, <b>MOF-5</b> and <b>ZIF-8</b>. The incorporation of the organometallic compounds in the resulting composites <b>[PtCl(L)]@ZIF-8</b>, <b>[PtCN(L)]@ZIF-8</b>, <b>[PtCl(L)]@MOF-5</b>, and <b>[PtCN(L)]@MOF-5</b> was verified by powder X-ray diffractometry, scanning electron microscopy, time-resolved photoluminescence spectroscopy and microscopy, as well as N₂- and Ar-gas sorption studies. The amount of encapsulated complex was determined by graphite furnace atomic absorption spectroscopy, showing a maximum loading of 3.7 wt %. If compared with their solid state forms, the solid-solution composites showed prolonged ³O₂-sensitive excited state lifetimes for the complexes at room temperature, reaching up to 18.4 μs under an Ar atmosphere, which is comparable with the behavior of the complex in liquid solutions or even frozen glassy matrices at 77 K.