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We report on the development of a fiber based oxygen sensor for power plant applications. The sensor utilizes quenching of the bright red fluorescence from inorganic molybdenum chloride (Mo6Cl12) clusters by ground state 3O2. We are developing a reflection mode fiber sensor by immobilizing the Mo6Cl12 clusters in an oxygen permeable sol-gel matrix at the far end of a Au clad high temperature silica fiber (continuous operation to 700 °C). In contrast to organic indicators these metal halide compounds are well-suited for oxygen sensing schemes in harsh environments. In this paper we report on the high temperature photophysical parameters of the Mo6Cl12 clusters obtained via absorption and emission spectroscopy in a controlled gas environment.