Fast and stable vapochromic response induced through nanocrystal formation of a luminescent platinum(II) complex on periodic mesoporous organosilica

Abstract

A hybrid vapoluminescent system exhibiting fast and repeatable response was constructed using periodic mesoporous organosilica with bipyridine moieties (BPy-PMO) and a Pt(II) complex bearing a potentially luminescent 2-phenylpyridinato (ppy) ligand. An intense red luminescence appeared when the Pt(II)-complex immobilised BPy-PMO was exposed to methanol vapour and disappeared on exposure to pyridine vapour. The ON-OFF vapochromic behaviour occurred repeatedly in a methanol/pyridine/heating cycle. Interestingly, a rapid response was achieved in the second cycle and cycles thereafter. Scanning and transmission electron microscopies (SEM/TEM), absorption and emission, and nuclear magnetic resonance spectroscopies, mass spectrometry, and powder X-ray diffraction indicated that methanol vapour induced Si-C cleavage and thus liberated [Pt(ppy)(bpy)]Cl (bpy = 2,2′-bipyridine) from the BPy-PMO framework. Furthermore, the self-assembling properties of the Pt(II) complex resulted in the formation of highly luminescent micro/nanocrystals that were homogeneously dispersed on the porous support. The unique vapoluminescence triggered by the unprecedented protodesilylation on exposure to protic solvent vapour at room temperature is attributable to BPy-PMO being a giant ligand and an effective vapour condenser. Consequently, this hybrid system presents a new strategy for developing sensors using bulk powdery materials.