Real-Time and In Situ Viscosity Monitoring in Industrial Adhesives Using Luminescent Cu(I) Phenanthroline Molecular...

Monitoring the viscosity of polymers in real-time remains a challenge, especially in confined environments where traditional rheological measurements are hard to apply. In this study, we have utilized the luminescent complex [Cu(diptmp)2]⁺ (diptmp = 2,9-diisopropyl-3,4,7,8-tetramethyl-1,10-phenanthroline) as an optical probe for real-time sensing of viscosity in various adhesives during the curing process (viscosity increases). The emission lifetime of the triplet metal-to-ligand charge transfer (³MLCT) state of [Cu(diptmp)₂]⁺ in epoxy adhesive increased exponentially during curing, similar to viscosity values obtained from oscillatory rheology. The longer lifetime in higher viscosity materials was attributed to changes in the excited-state deactivation processes from a known Jahn-Teller distortion in the Cu(I) geometry from tetrahedral in the ground state to square planar in the excited state. The real-time viscosity was also monitored reversibly by emission lifetime during polymer swelling (viscosity and lifetime decrease) and unswelling (viscosity and lifetime increase). Monitoring emission lifetime, unlike measuring the excited-state lifetime via transient absorption measurements in our previous study, allowed us to measure viscosity in opaque samples which scatter light. The optical probe [Cu(diptmp)₂]⁺ in Gorilla Glue adhesive showed a clear correlation of the emission intensity or lifetime to viscosity during the curing process. We have also compared these lifetime changes using [Ru(bpy)₃]²⁺ (bpy = bipyridine) as a control. [Cu(diptmp)₂]⁺ showed not only a higher emission lifetime but also more ubiquity as a real-time viscosity sensor.