Luminescent nanoclusters of linear dicyanoargentate(I) ions doped in different alkali halide single crystals (NaF, NaCl, NaBr, and KCl) have been investigated. Site-selective excitation of the different nanoclusters results in the appearance of emission bands which are assigned to different luminescent {[Ag(CN)2]−}
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nanoclusters in the host lattices. The nanoclusters of [Ag(CN)2]− in the alkali halides display energy tunability over a wide wavelength interval. The ab initio DFT calculations show that for nanoclusters, the first excited state has a deeper potential and shorter internuclear separation than the nanocluster ground state, indicative of excimer/exciplex behavior. Molecular modeling indicates how the distribution of nanoclusters varies with the host lattice. This emission energy tunability makes these systems attractive candidates for potential applications, such as tunable solid state lasers, photocatalysts, and photosensitizers for water splitting.