Ultrafast optical modulation of vibrational strong coupling in ReCl(CO) ₃ (2,2‐bipyridine)

Abstract Polaritons – hybrid light‐matter states formed from the strong coupling of a bright molecular transition with a confined photonic mode – may offer new opportunities for optical control of molecular behavior. Vibrational strong coupling (VSC) has been reported to impact ground‐state chemical reactivity, but its influence on electronic excited‐state dynamics remains unexplored. Here, we take a first step towards excited‐state VSC by demonstrating optical modulation of the ReCl(CO) 3 (bpy), (bpy = 2,2‐bipyridine) complex under VSC using femtosecond ultraviolet (UV)‐pump/infrared (IR)‐probe spectroscopy. We establish ground‐state VSC of ReCl(CO) 3 (bpy) in a microfluidic Fabry‐Pérot cavity equipped with indium tin oxide (ITO)‐coated mirrors. ITO is effectively dichroic as it is reflective in the IR and transmissive in the UV‐visible and therefore minimizes optical interference. Excitation with UV pump light drives ReCl(CO) 3 (bpy) into a manifold of electronic excited states that subsequently undergo non‐radiative relaxation dynamics. We probe the transient response of the strongly‐coupled system in the mid‐IR, observing both Rabi contraction and cavity‐filtered excited‐state absorption signatures. We reconstruct the intrinsic response of intracavity molecules from the transient cavity transmission spectra to enable quantitative comparison with extracavity control experiments. We report no changes in the excited‐state dynamics of ReCl(CO) 3 (bpy) under ground‐state VSC. However, we do observe significant amplification of transient vibrational signals due to classical cavity‐enhanced optical effects. This effort lays the groundwork to pursue direct excited‐state VSC aimed at modulating photochemical reactivity.