Structural resilience in organic–inorganic stacked assemblies: sulfur-mediated self-compensating interaction and metal identity masking in group 10 dithiocarbamate cocrystals with tetracyanobenzene

Abstract

This work investigates the relative influence of metal identity versus ligand environment in determining supramolecular architecture of stacked hybrid organic–inorganic systems. We demonstrate a sulfur-mediated self-compensating mechanism that masks metal-specific electronic differences, enabling ligand-controlled assembly over conventional metal-directed organization. Through systematic investigation of group 10 metal dithiocarbamate cocrystals [M(S₂CNR₂)₂] (M = Ni, Pd, Pt; R₂ = alkyl) with 1,2,4,5-tetracyanobenzene, we reveal structural resilience—identical parallel-displaced supramolecular architectures are maintained across the entire Ni–Pd–Pt triad despite fundamental differences in d_z²-orbital nucleophilicity that typically govern such assemblies. This contradicts established principles where metal variation should produce distinctly different structural outcomes. Comprehensive quantum chemical analysis using QTAIM, IGM, ETS-NOCV, and energy decomposition methods reveals that S atoms from the dithiocarbamate ligands actively neutralize inherent metal-specific properties, creating electronically equivalent {MS₄} building blocks. Despite different metals, remarkably consistent interaction energies (−40.6 to −42.8 kcal mol⁻¹) and metal contributions (13.9–15.9%) demonstrate functional equivalence in the supramolecular recognition. Our study establishes ligand-mediated metal identity masking as a design principle for creating structurally predictable metal-involving materials regardless of metal center.