High-spin states in the proton-rich nucleus ⁴⁵V have been identified for the first time. A comprehensive gamma-ray decay scheme has been established following an experiment performed at the Vivitron accelerator at IReS Strasbourg by using the Euroball gamma-ray detector array coupled to the Neutron Wall and Euclides detector arrays. The natural (negative-) parity scheme is identified up to the f_7/2 band termination in addition to a positive-parity collective structure based on a d_3/2 particle-hole excitation. Comparison of this scheme with that of the mirror partner, ⁴⁵Ti, has yielded detailed information on the variation of Coulomb energy as a function of excitation energy and angular momentum. This is the first time that such an analysis has been performed for a collective structure built on a cross-shell excitation. Comparison of the observed Coulomb energies with those predicted by large-scale shell-model calculations is presented. In this case, unusually, the calculations do not fare as well as for heavier nuclei in the shell. In addition, stark differences between the two nuclei are observed for the decay intensities of the parity-changing E1 decays that de-excite the positive-parity deformed bands.