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Low‐valent main group compounds that fluoresce in the solid‐state were previously unknown. To address this, we investigated room‐temperature photoluminescence from a series of crystals of germylenes 3–8 in this article; they exhibited emissions nearly reaching the NIR. Germylene carboxylates (3–8) were synthesized by reacting dipyrromethene stabilized germylene pyrrolide (2) with carboxylic acids...