Fine-Tuning X-Ray Sensitivity in Organic-Inorganic Hybrids via an Unprecedented Mixed-Ligand Strategy

Crystalline organic-inorganic hybrids, which exhibit colorimetric responses to ionizing radiation, have recently been recognized as promising alternatives to conventional X-ray dosimeters. However, X-ray-responsive organic-inorganic hybrids are scarce and the strategy to fine-tune their detection sensitivity remains elusive. Herein, an unprecedented mixed-ligand strategy is reported to modulate the X-ray detection efficacy of organic-inorganic hybrids. Deliberately blending the stimuli-responsive terpyridine carboxylate ligand (tpc^- ) and the auxiliary pba^- group with different ratios gives rise to two OD thorium-bearing clusters (Th-102 and Th-103) and a 1D coordination polymer (Th-104). Notably, distinct X-ray sensitivity is evident as a function of molar ratio of the tpc^- ligand, following the trend of Th-102 > Th-103 > Th-104. Moreover, Th-102, which is exclusively built from the tpc^- ligands with the highest degree of π-π interactions, exhibits the most sensitive radiochromic and fluorochromic responses toward X-ray with the lowest detection limit of 1.5 mGy. The study anticipates that this mixed-ligand strategy will be a versatile approach to tune the X-ray sensing efficacy of organic-inorganic hybrids.