Infrared photodissociation spectroscopy in the N-N stretching region is reported for gas-phase Nb+(N-2)(n) complexes (n = 3-16). The coordination of nitrogen to the metal cation causes the IR-forbidden N-N stretch of N-2 to become active in these complexes. Fragmentation occurs by the loss of intact N-2 molecules, and the yield as a function of laser wavelength produces an IR excitation spectrum. The dissociation patterns indicate that Nb+ has a coordination of six ligands. The infrared spectra for all complexes contain bands red-shifted from the N-N stretch in free nitrogen, consistent with ligand-metal charge-transfer interactions such as those familiar for metal carbonyl complexes. Using density functional theory, we investigated the structures and ground electronic states for each of the small cluster sizes. Theory indicates that binding to the low-spin triplet excited state of the metal ion becomes progressively more favorable than binding to its high-spin quintet ground state as additional ligands are added to the cluster. Although the quintet state is the ground state for the n = 1-4 complexes, IR spectroscopy confirms that the low-spin triplet electronic state becomes the ground state for the n = 5 and 6 complexes. The n = 4 complex has a square-planar structure, familiar for high-spin d(4) complexes in the condensed phase. The n = 5 complex has a geometry that is nearly a square pyramid, while the n = 6 complex has a structure close to octahedral.