Antimony(iii) halide based zero dimensional hybrids have gained attention as broadband emitters. Until now, quadrangular pyramidal SbX5 based and octahedral SbX6 based 0D hybrids have been reported utilizing different organic ligands demonstrating some structural tunability affecting their emissive properties. Utilizing a common organic ligand, here we demonstrate the structural tunability (quadrangular pyramidal, octahedral, or a combination thereof) of the metal halide unit in Sb(iii)Cl 0D hybrids with contrasting photo-physical properties (broadband, Stokes shift, strong/weak colored emission). The structure-property-mechanism correlation of the synthesized compounds [1 (C12H52Cl18N8O4Sb3; tris Sb green); 2 (C12H50Cl14N8O3Sb2; tris Sb red); 3 (C24H88Cl25N16O4Sb3; tris Sb yellow)] identifies crucial factors that control their emissive properties. The X-ray analysis reveals the structure (1-octahedral; 2-quadrangular pyramidal; 3-combination thereof) and the order of the extent of structural distortion as 1-3 MUCH LESS-THAN 2. The metal halide coordination environment asymmetry and its structure are observed to dictate PL emission energy (1-green; 2-red; 3-yellow) as supported by a qualitative Molecular Orbital scheme. The extent of structural distortion guides the observed Stokes shifts (1-165 nm; 2-290 nm; 3-200 nm; 1-3 < 2). Interestingly, the extent of distortion is found to be well correlated with the observed PLQY (1-45%; 2-6%; 3-43%; 1-3 >> 2). This report clearly demonstrates the structural tunability and the effect of the metal halide unit structure/distortion in shaping the emissive properties of 0D organic Sb(iii) halide hybrids.

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