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In a high‐resolution photoelectron imaging and theoretical study of the IrB3− cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B3 ring coordinated with the Ir atom. The isomer with the higher EA consists of a B3 ring with a bridge‐bonded...
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