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The search for new functional materials with tunable properties remains a central challenge in chemistry, particularly for applications in energy and electronics. In this work, we present a framework for predictive crystal design in alkali metal chalcogenides that enables controlled dimensional reduction of a parent covalent motif, yielding a broad range of electronic structures, which systematically evolve from one parent to the other. We present 11 new members of the AnCu4–nSnS4 family (A = alkali metal; n = 0–4), which reduce the three-dimensional (3D) covalent network of Cu4SnS4 into various 3D, 2D, 1D, and 0D [Cu4–nSnS4]n− motifs through the substitution of Cu with alkali metals of various radii. The end members of the family set the range in achievable band gaps at 0.99 eV for fully covalent Cu4SnS4 (n = 0) and 3.38 eV for K4SnS4 (n = 4) with 0D [SnS4]n− tetrahedra. As the dimensionality of [Cu4–nSnS4]n− systematically reduces within AnCu4–nSnS4 (n = 1–3), a stepwise increase in band gap energy occurs through a gradual decrease in the energy of the valence band maximum and an increase in the conduction band minimum, with an increase in the effective masses of charge carriers. Furthermore, irrespective of the alkali metal, the thermal stability decreases with decreasing [Cu4–nSnS4]n− dimensionality within the quaternary members. Most importantly, we demonstrate that predictable crystal structure and property evolution for a given composition space is possible by deriving a general formula based on substituting the covalent metals of a parent structure with alkali metals. 

We report the two-dimensional (2D) bimetallic selenophosphate, LiGaP2Se6, prepared through direct combination reactions and P2Se5 flux methods. The material is a member of the broad class of van der Waals 2D materials of the type M2P2Q6 (M = metals). The structure was determined using single-crystal X-ray diffraction and refined in the chiral space group P3̅1c, with lattice parameters a = b = 6.2993(9) Å, c = 13.308(3) Å, α = β = 90°, γ = 120°. Differential thermal analysis indicated a congruent melting point at ∼458 °C. Optoelectronic properties were assessed using ultraviolet–visible (UV–vis) spectroscopy, showing a band gap of 2.01 eV, and photoemission yield spectroscopy in air (PYSA), which determined a work function of 5.44 eV. Notably, stability studies on LiGaP2Se6 revealed remarkable resilience despite its Li content, showing no structural changes after 2 weeks in ambient air or after soaking in a water/ethanol bath.