Homoleptic [L–I–L]⁺ iodine(I) complexes (where L = prochiral NR¹R²R³ tertiary amine) were synthesized via the [L–Ag–L]⁺ → [L–I–L]⁺ cation exchange reaction. In solution, the pseudo-enantiomorphic amines form a “locked” iodine(I) complex, [R¹R²R³N-I-NR¹R²R³]⁺, where the two prochiral amines became become chiral with opposite absolute configurations of the sp³-nitrogen forming meso-[L–I–L]⁺ halogen(I) complexes. Unlike the [L–Ag–L]⁺ silver(I) precursor complexes with meso-configuration, characterized by single crystal X-ray crystallography, the corresponding iodine(I) analogues are not stable in solid-state due the their high reactivity. Density functional theory (DFT) calculations are used to compute the Ag⁺–N and I⁺–N bond energies, and to study the C_π···I⁺ and C–H···I⁺ interactions between the N-alkyl and N-aryl groups and the iodine(I) cation expected to stabilize these complexes.