A series of four isomorphous, 1:2 (complex/) rare cocrystals of coordination compounds of Ln(III) ions as [Ln()(NO)(HO)][] (Ln(III) = Gd (), Tb (), Dy (), and Ho ()), were synthesized with ,-diisobutylisonicotinamide () using a metal-to-ligand ratio of 1:1. All compounds are dimeric in nature with two cocrystallized molecules centro-symmetrically interspersed between two dimeric units with H-bonded bridges between them to form interesting, self-assembled H-bonded tapes along the -axis. Detailed Shape analysis and Hirshfeld analysis are done to demonstrate geometry around the metal centers and various noncovalent interactions present in the systems, respectively. Magnetic studies show that compound is a field-induced single-molecule magnet (SMM) for which the magnetization relaxes through a combination of Orbach (Δ = 51 K and τ = 3.1 × 10 s) and Raman mechanisms. Solid-state luminescence studies reveal that compounds , , and are photoluminescent in the visible range, while exhibits luminescence in the NIR region. Compound shows cold white-light emission with Commission Internationale de l'Eclairage (CIE) coordinates (0.31, 0.30) and correlated color temperature (CCT) value of 6942 K.