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The blue color of Na2[Co(SCN)4] arises from a d-d transition within the cobalt(II) ion (Co²⁺). Specifically, the transition involves the excitation of an electron from a lower energy d orbital (t2g) to a higher energy d orbital (eg) within the octahedral coordination complex. The energy difference between these orbitals corresponds to the absorption of light in the orange-red region of the visible spectrum, leading to the complementary blue color observed.