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. [ABSTRACT FROM AUTHOR]