where ci corresponds to the color of particle i, δ(n,m) is the Kronecker delta, and ULJ(r,ε) is the standard 12-6 LJ potential with σ = 1 and minimum energy at -ε. The summation over the energies of all unique pairs of colored particles gives the potential energy of the system, as E = Σi<jVi,j(r). This is equivalent to the summation over all pairwise energies between particles that form interfaces, due to the designed exclusion of interactions between colored particles on the same block (i.e., Vi,j = 0 if i and j are on the same block). The lowest energy is thus achieved only for a complete and correct structure, Emin = -nε, where n is the number of interfaces in the target structure, and all interfaces are formed from particles of matching colors, ci = cj, separated at their optimal LJ distance of r0 = 2 1/6 . First, we map the (T,ε')-domain where the complete one-pot self-assembly of a single chain of N distinguishable square blocks is possible. The quality of the resultant structure is judged based on its completeness, i.e., the length of the assembled structure divided by N, and its correctness, i.e., the fraction of correct interfaces within the cluster. These are used here to define an addressability score ɑ = (completeness × correctness), evaluated at the end of a simulation. Three categories are introduced to describe the sampling outcome based on the addressability scores: (i) addressable, indicating a successfully assembled target structure (ɑ = 1), (ii) partial, indicating that some portions of the target structure were successfully assembled (0.8 ⩽ ɑ ⩽ 0.99), and (iii) failed, indicating that the blocks were unable to bind and/or the developed structure contains multiple incorrect interfaces (ɑ < 0.8). For illustration, ɑ(T,ε') is sampled for a chain of N = 10. This reveals a limited (T,ε')-domain, bounded by T ≃ constant (const) ≡ Tc, and T/ε' ≃ const, where individual components can be successfully assembled into a completely addressable (ɑ = 1) structure (Figure ). At T > Tc the assembled structures are correct, but incomplete, unable to reach the desired target size of N = 10. This suggests that native bonds are unstable for T > Tc, akin to melting: the energy gain (-ε) in forming correct bonds is less than the entropic cost associated with such assembly, < TΔs, implying Tc = -ε/Δs. The weak sensitivity of Tc to changes in ε', along with the appearance of only correct bonds at the final simulation state above this limit (Figure ), confirms the instability of ε bonds above Tc. Thus Tc serves as the "ceiling temperature", above which assembly is impossible. This is analogous to the balance between entropy and enthalpy (ΔHp) governing the Tc for addition polymerization through Dainton's equation, Tc ~ -|ΔHp|/ln(⍴) or Tc/|ΔHp| ~ 1/ln(V), where ⍴ and V are the monomer concentration and system volume. Notably, this equation suggests that Tc should increase with increasing concentration, which is also seen in our simulations utilizing different block area concentrations, ⍴ = N Ap/A (Ap and A are the areas of one block and of simulation box). For example, the Tc for a chain of N = 10 is higher at ⍴ = 0.04 compared to ⍴ = 0.01 (Figure ). However, our particles are distinguishable in contrast to the indistinguishable monomers in addition polymerization, which entails that each particle incorporated into the growing structure is associated with an additional entropy cost of Δsdist ~ -ln(N!)/N. Thus, a lower Tc is expected for structures with larger N, as observed in our simulations: Tc for a chain of N = 20 is lower than that of a chain of N = 10 at the same ⍴ = 0.01 (Figure ).