Achieving UV and X‑ray Dual Photochromism in a Metal–Organic Hybrid via Structural Modulation

Rational design and synthesis of new photochromic sensors have been active research areas of inquiry, particularly on how to predict and tailor their properties and functionalities. Herein, two thulium 2,2′:6′,2′′-terpyridine-4′-carboxylate (TPC)-functionalized metal–organic hybrids, Tm­(TPC)2(HCOO)­(H2O) (TmTPC-1) and Tm­(TPC)­(HCOO)2 (TmTPC-2) with different photochromic response behaviors, have been successfully prepared, allowing for straightforward investigations of the structure–property correlation. Single-crystal X-ray diffraction and electron paramagnetic resonance analyses revealed that the incorporation of a unique dangling decorating TPC unit in TmTPC-1 offers a shorter and more accessible π–π interaction pathway between the adjacent TPC moieties than that in TmTPC-2. Such a structural feature leads to the production of radical species via a photoinduced intermolecular electron-transfer (IeMCT) process upon UV or X-ray irradiation, which ultimately endows TmTPC-1 with a rather unusual UV and X-ray dual photochromism. A linear relationship between the change of UV–vis absorbance intensity and X-ray dose was established, making TmTPC-1 a promising dosimeter for X-ray radiation with an extremely high energy threshold (30 kGy). To advance the development for real-world application, we have fabricated polyvinylidene fluoride (PVDF) membranes incorporating TmTPC-1 for functioning either as a UV imager or as an X-ray radiation indicator. Lastly, TmTPC-1 exhibits high thermal stability (up to 400 °C) and radioresistance (at least 900 kGy), and also excellent reversibility of photochromic transformation (at least 5 cycles).