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Achieving UV and X-Ray Dual Photochromism in a Metal–Organic Hybrid Via Structural Modulation

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Achieving UV and X-Ray Dual Photochromism in a Metal–Organic Hybrid Via Structural Modulation www.acsami.org Research Article Achieving UV and X‑ray Dual Photochromism in a Metal−Organic Hybrid via Structural Modulation Huangjie Lu, Zhaofa Zheng, Zi-Jian Li, Hongliang Bao, Xiaojing Guo, Xiaofeng Guo, Jian Lin,* Yuan Qian, and Jian-Qiang Wang Cite This: ACS Appl. Mater. Interfaces 2021, 13, 2745−2752 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: 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 para- magnetic 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). KEYWORDS: photochromism, metal−organic hybrids, UV, X-ray, dosimetry, structural modulation − ■ INTRODUCTION ionization radiations.17 22 The photoinduced color transition of a single chemical species upon cumulative dose allows for Ultraviolet and ionization radiations are extensively used for fi 23−25 industrial and medical purposes, including lithography, food direct quanti cation of visually undetectable radiations. 1−3 Moreover, the reversibility of photochromism makes such processing, disinfection, diagnostics, therapeutics, etc. See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles. materials reusable, which is a key merit for real-world Downloaded via SHANGHAI INST OF APPLIED PHYSICS on February 1, 2021 at 01:42:52 (UTC). However, excessive doses of UV and ionization radiation, application. Organic photochromic materials, for example, being mutagens, can impose health threats and result in 4,5 azobenzene, viologen, and diethylene, have been documented, different types of cancer. To reduce corresponding health but their relatively low chemical and thermal stabilities make risks, radiation sensors with direct read-out property for them unsuitable for practical applications.26 Inorganic photo- visually monitoring radiation are highly desirable. However, chromic metal oxides and halides are inherently advantageous many radiation sensors do not display direct and visual in terms of resistance to fatigue; however, the number of these inspection of radiation dosage. For instance, radio-photo- materials is limited and many of them are hygroscopic.27 The luminescence (RPL) materials require spectrophotometers to − combination of metal centers with photoactive ligands in read the converted incident signal.6 8 Semiconductor detectors metal−organic hybrids endows the materials with decent and thermoluminescent dosimeters (TLD) require electronic accessories to read the incident signal and can malfunction − under harsh conditions.9 12 Other radiation sensors, such as Received: November 10, 2020 scintillators, quantify only instantaneous radiation rather than Accepted: December 28, 2020 accumulative dose, which is not suitable for application under Published: January 6, 2021 − certain circumstances.13 16 Photochromic materials represent one of the most promising candidates for visible and sensitive sensing of UV and © 2021 American Chemical Society https://dx.doi.org/10.1021/acsami.0c20036 2745 ACS Appl. Mater. Interfaces 2021, 13, 2745−2752 ACS Applied Materials & Interfaces www.acsami.org Research Article Figure 1. (a) Coordination environment of the Tm3+ cation in TmTPC-1. (b) One independent 1D chain of TmTPC-1 composed of both bridging and decorating TPC units. (c) Representation of the structure of TmTPC-1. (d) Coordination environment of the Tm3+ cation in TmTPC-2. (e) One independent 1D chain of TmTPC-2 solely composed of bridging TPC units. (f) Representation of the structure of TmTPC-2. Color code: Tm in green, O in red, N in blue, and C in gray. chemical and thermal stabilities, as well as high detection Tm/TPC metal−ligand ratio (1:1) than that (1:2) of − sensitivity.28 32 Furthermore, the highly designable and TmTPC-1. The phase purities of bulk samples were confirmed variable topologies of metal−organic hybrids can give rise to by powder X-ray diffraction (PXRD) and their element materials with unprecedented properties, which were not components were analyzed by SEM-EDS as shown in Figures − realized in either purely inorganic or organic complexes.33 40 S1 and S2, respectively. However, photochromic metal−organic hybrids, especially the Single-crystal X-ray diffraction analysis revealed that ones sensitive to ionization radiations, remain uncommon and TmTPC-1 crystallizes in monoclinic space group P21/c, a large number of them are limited to viologen-templated − whereas TmTPC-2 features a P2/c space group in a lower complexes.24,30,41 46 Therefore, expanding the families of symmetry (Table S1). The asymmetry unit of TmTPC-1 photochromic materials is highly needed. contains one crystallographically independent Tm3+ cation, − In the present work, we demonstrate a structural modulation two TPC units, one HCOO anion, and one H2O molecule, approach to realize UV and X-ray dual reversible photo- while one unique 1/2 Tm3+ cation, one 1/2 TPC, and one chromism in a terpyridine-functionalized metal−organic HCOO− anion can be found in TmTPC-2.Tm3+ ions in both hybrid. Reversible photochromic transitions from colorless to complexes are nine-coordinated with three N and six O atoms. dark green occur either upon UV or X-ray irradiation for The coordination sphere of Tm3+ in TmTPC-1 is donated − Tm(TPC)2(HCOO)(H2O) (TmTPC-1), in contrast to Tm- from three TPCs, one HCOO anion, and one coordinating 3+ (TPC)(HCOO)2 (TmTPC-2), which exhibits no obvious H2O molecule as shown in Figure 1a and Table S2. The Tm μ color change under identical conditions. A rather unique polyhedra are interconnected alternatively by a bridging 2- mechanism of intermolecular electron transfer (IeMCT) η2,η3 TPC anion, forming a chain topology extending along the π−π driven by enhanced interactions between the decorating c axis (Figure 1b). The other TPC anion, however, functions as TPC moieties of TmTPC-1 upon irradiation was revealed. a decorating unit, whose carboxylate site coordinates with one Thus, TmTPC-1 can function as a dosimeter for high dose Tm3+ cation in a η2-terminal bidentate mode. The neighboring fl radiation and be further fabricated into exible membranes as a 1D chains are packed together via intermolecular π−π radiation imager and an indicator. interactions and van der Waals interactions between the decorating TPC anions to form an interdigital structure ■ RESULTS AND DISCUSSION (Figure 1c). In TmTPC-2, the Tm3+ cation is coordinated − Synthesis and Structure. Solvothermal reactions between with two TPC and two HCOO anions (Figure 1d and Table ′ ′ ′′ ′ μ η2 η3 fi Tm(NO3)3 and 2,2 :6 ,2 -terpyridine-4 -carboxylic acid S3). Only the 2- , TPC bridging unit can be identi ed, (HTPC) with the absence and presence of concentrated which connects to the Tm3+ polyhedra and leads to the HClgaverisetotwodistinctmetal−organic hybrids, assembly of a 1D chain structure projecting along the b axis Tm(TPC)2(HCOO)(H2O) (TmTPC-1) and Tm(TPC)- (Figure 1e). Intermolecular interactions exist between the (HCOO)2 (TmTPC-2), respectively. The hydrochloric acid bridging TPC moieties of the adjacent chains to expand and functions as a modulator for the synthesis of TmTPC-1 and stabilize the overall architecture (Figure 1f). TmTPC-2. The presence of HCl inhibits the deprotonation of Dual Photochromic Properties. Upon being exposed to HTPC, making the TPC ligand less available during the UV radiation (365 nm, 2 mW), TmTPC-1 exhibited a striking synthesis of TmTPC-2. Consequently, TmTPC-2 has a larger photochromic transition from colorless to dark green as shown 2746 https://dx.doi.org/10.1021/acsami.0c20036 ACS Appl. Mater. Interfaces 2021, 13, 2745−2752 ACS Applied Materials & Interfaces www.acsami.org Research Article in Figure 2a. TmTPC-2, however, showed a negligible color performed for at least five consecutive cycles without obvious change despite the fact that it consists of similar chemical degradation, implying excellent photostability of TmTPC-1 (Figure S5). For examination of the photochromic behavior upon ionization radiations, TmTPC-1 was illuminated by a W Kα or a Cu Kα X-ray source with a radiation dose rate of 26.5 or 120 Gy/min, respectively. TmTPC-1 exhibited a sensitive response to X-ray via a similar color change from colorless to dark green (Figure 2d). The emergence of new bands can again be observed in the visible range. However, the absorption peak at 362 nm had a much more dramatic intensity reduction than the one recorded under UV irradiation. Such a feature can be utilized for X-ray dosimetry (Figure 2e). The absorbance − change (A0 A)/A0% as a function of radiation dose (D) was plotted in Figure 2e, where A0 is the initial absorbance intensity at 362 nm and A is the absorbance intensity upon X- ray irradiation.
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