As science focuses on the finer details of complex processes occurring in biology, the need for tools responsive to researcher control have become critical to communicate with cellular functions in both a spatial and temporal manner. To this end, light responsive “caging groups” have been used to generate molecular constructs with which researchers can activate using directed irradiation to elicit biological responses where and when they want. This advancement in molecular control has greatly improved our ability to study biological systems in their dynamically intricate form. Most of these photoresponsive moieties perform well within a petri dish, but their application is limited in vivo. Current photochemical tools require high energy light for their activation. Dermal tissue contains bio chromophores that absorb this light and prevents its penetration to less than a few millimeters making photoactivation impossible. However, tissue has an “optical window” in the red and near infrared (600 – 1000 nm) where light penetrates efficiently to clinically relevant depths. Therefore, researchers have sought long wavelength responsive caging groups but have had little success to date. Herein, I report the development of an entire class of red and near infrared responsive (600 – 800 nm) caging groups based on Vitamin B12 or cobalamin. Upon modification with a fluorophore antenna, these metal complexes can capture long wavelength light to perform photochemical work in the form of bond scission reactions. The effect is compatible with a range of fluorophores covering the entire near infrared spectrum, and bond scission proceeds rapidly with extremely high efficiencies. In this work, the initial development and characterization of these molecules as photoactivateable groups will be discussed. Furthermore, I will demonstrate how these molecules can be applied for clinical applications, such as drug delivery and tissue scaffold formation, to provide safer and less invasive treatments.