Copper(I) iodide and other copper(I) salts (CuX) react with amines and sulfides (L) in their gas phase to form luminescent rhomboid Cu2(�2-X)2L4 and/or cubane Cu4(�3-X)4L4 complexes. This work reports this spontaneous reaction occuring at the surface of CuI powder, pressed CuI pellets, CuI-impregnated polymer films, and CuI-embedded polypropylene plates. An LED fiber optic fluorimeter was used to monitor the reaction of gaseous pyridine (Py) or other nucleophile with CuI-impregnated PVC films. Known Py vapor pressures were established in a sealed chamber through gas-phase dilutions and correlated to luminescence emission response. Detectability of Py was established at vapor pressures as low as 0.001 Torr. Surface phases of CuI-Py were identified through X-ray powder diffraction. Initial formation of dimer Cu2(�2-I)2Py4 (emission l = 520 nm) quickly gives way to tetramer Cu4(�3-I)4Py4 (emission l = 580 nm)
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