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 Huangjie Lu, Zhaofa Zheng, Zi-Jian Li, Hongliang Bao, Xiaojing Guo, Xiaofeng Guo, Jian Lin,* Yuan Qian, and Jian-Qiang Wang

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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 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). 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

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. A good linear relationship was found between − 48 D/[((A0 A)/A0] and D (Figure 2e). Such a correlation can be employed for the X-ray dosimetry over a wide dynamic dose range up to 30 kGy. This is a great advancement of RPL applications as its energy threshold is significantly higher than 10 kGy of SCU-200, which was the record for RPL materials.49 Photochromism Mechanism. To elucidate the mechanism of photochromism, we employed PXRD and FTIR studies and showed that the structures and chemical constituents remained unchanged before and after irradiation for both complexes, demonstrating that the photochromic transition is irrelevant with structural transformation or photolysis, as observed in many organic materials (Figures Figure 2. (a) In situ color transitions of TmTPC-1 and TmTPC-2 S1 and S6).50 Electron paramagnetic resonance (EPR) upon 365 nm UV irradiations. (b) Time-dependent UV−vis spectroscopy studies suggested that TmTPC-1 and TmTPC- absorbance spectra of TmTPC-1 upon 365 nm UV irradiation. (c) 2 were EPR silent before irradiation (Figure 3a). New EPR Time-dependent UV−vis spectra of TmTPC-2 upon 365 nm UV − signals with g factors of 2.0032 and 2.0098 appeared after UV irradiation. (d) Photochromism of TmTPC-1 and the UV vis and X-ray irradiations, respectively, for TmTPC-1, suggesting absorbance spectra of TmTPC-1 upon continuous X-ray irradiation. •− 51 − − the generation of TPC radical species. However, no (e) Correlation between (A0 A)/A0 and X-ray dose (0 30 kGy). − obvious EPR signals can be observed for TmTPC-2 after either Inlet: correlation between D/[(A0 A)/A0] and X-ray dose with a linear fitting. UV or X-ray irradiation (Figure 3b). Radical species (g = 2.0018) can be generated only after an extremely high dose (900 kGy) of γ irradiation, which agrees well with its slow components as TmTPC-1.Thetime-dependentUV−vis response of photochromic behavior. These results led to the absorbance spectra were collected on single crystals of hypothesis that the photochromism originates from the TmTPC-1 and TmTPC-2 using a microspectrometer. A series production of radical species through a photoinduced of fingerprint bands of Tm3+ at 470, 666, 691, and 795 nm for electron-transfer process.43,50,52 both unirradiated complexes were identified, corresponding to Meticulous structural comparisons between TmTPC-1 and − 3 → 1 3 3 3 the 4f 4f transitions of H6 G4, F2, F3, and H4, TmTPC-2 before and after UV or X-ray irradiation were respectively (Figures 2b,c).47 For TmTPC-1, two broad bands conducted by SCXRD on single crystals using the same emerged at 400−470 and 575−675 nm with increasing protocol (measurement angles and exposure time) and under intensities; correspondingly, the color of the crystal became identical temperatures. The unit cell dimensions of TmTPC-1 darker upon continuous UV irradiation. In contrast, the peak experienced slight shrinking (0.21% and 0.29% for unit cell centering in the UV range (361 nm) and bands at 760−800 volume), implying more compact molecular packings after UV nm diminished slightly as a function of accumulated radiation and X-ray irradiations (Table 1). However, those parameters of dose. Compared to TmTPC-1, TmTPC-2 showed a much TmTPC-2 exhibited approximately 0.16% and 0.15% slower response to the UV radiation in the visible ranges of expansions under comparable conditions. Moreover, for the 400−470, 575−675, and 770−800 nm, which is consistent decorating TPC of TmTPC-1, the π−π distances between the with its lack of visible color transition. It is noteworthy that the centers of the pyridyl group on one TPC unit to the green color of TmTPC-1 remains unchanged under ambient neighboring pyridyl plane of another TPC unit decrease conditions for at least 5 days, as confirmed by its time- from 3.495 to 3.483 Å and from 3.489 to 3.475 Å after UV and dependent UV−vis absorbance spectra and unchanged UV−vis X-ray irradiations, respectively (Figure 3c,e). Meanwhile, slight absorbance intensities at 450 nm (Figure S3). This property shrinkages of the interlamellar π−π distances (from 3.584 to makes TmTPC-1 particularly suitable for radiation dosimetry. 3.577 Å and from 3.583 to 3.579 Å after UV and X-ray The color can be bleached by heating the material at 120 °C irradiations, respectively) of the bridging TPC units in for 3 days, implying the reversibility of photochromism TmTPC-1 were observed. In contrast, those of the bridging transformation (Figure S4). Such a reversible switch can be TPC ligands of TmTPC-2 varied from 3.504 to 3.506 Å and

2747 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

Stability Study. TmTPC-1 and TmTPC-2 feature suprisingly high radiolytic and thermal stabilities despite their 1D nature in terms of structure. Their radioresistances were inspected by exposing polycrystalline samples under γ-rays with a dose rate of 11.8 kGy/h. PXRD analysis revealed that the structures of both complexes remained unchanged upon an accumulated dose of 900 kGy (Figure S1). This endows TmTPC-1 as one of the most radioresistant metal−organic hybrids and makes it particularly suitable for high-dose (kGy − level) ionization radiation sensing.56 59 Furthermore, thermogravimetric analysis (TGA) revealed that TmTPC-1 and TmTPC-2 are stable up to 400 and 380 °C, respectively, demonstrating excellent thermal stabilities of both complexes (Figure S7). In addition, PXRD studies further revealed that the structure of TmTPC-1 remains intact under different relative humidity conditions (35%, 55%, 75%, and 95%) and temperatures (100, 200, and 300 °C) (Figures S8 and S9). These outstanding chemical, radiolytic, and thermal stabilities could be associated with the π−π interactions between the conjugated TPC.60 TmTPC-1@PVDF Membrane Fabrication. The bulk powder form of TmTPC-1 is not desirable for real-world applications, for example, radiation dosimetry and medical imaging, which require the materials to be processed into certain shapes. Fabricating metal−organic hybrids with polyvinylidene fluoride (PVDF) polymer into flexible membranes has been demonstrated to be a feasible approach because the crystallinity and physiochemical properties of metal−organic hybrids can be well retained in PVDF. Figure 3. (a) EPR spectra of TmTPC-1 before and after UV and X- Therefore, a TmTPC-1@PVDF membrane for UV detection ray irradiations. (b) EPR spectra of TmTPC-2 before and after UV, was developed on the basis of the method reported by Wang X-ray, and γ irradiations. (c) Representations showing the π−π and co-workers.61 As shown in Figure 4a, the color of the interactions of decorating and bridging TPC ligands in TmTPC-1. π−π membrane is initially white; and a tin foil engraved with a (d) Representations showing the interactions of bridging TPC radiation symbol was placed onto the membrane. After the ligands in TmTPC-2. (e) π−π interaction fragment models of decorating and bridging TPC ligands in TmTPC-1.(f)π−π membrane was irradiated with UV, the radiation symbol in interaction fragment model of bridging TPC ligands in TmTPC-2.. green color can be clearly distinguished from the background of the membrane by naked eyes (Figure 4a). Alternatively, the TmTPC-1@PVDF membrane can be further utilized as a from 3.500 to 3.504 Å after UV and X-ray irradiations, radiation indicator for X-ray beam alignment. After exposure to respectively (Figure 3d,f). The additional degree of freedom donated from the decorating TPC ligands in TmTPC-1 allows the synchrotron X-ray at Shanghai Synchrotron Radiation for enhanced π−π interactions and correspondingly provides a Facility (beamline BL14W1) for 10 s, the irradiated area μ more accessible intermolecular electron-transfer (IeMCT) exhibited a dark green spot with a dimension of 400 m, which 33,53,54 μ pathway than TmTPC-2. This feature gives rise to the is comparable to the size of the beam size (300 m) and larger absorption bands of the π → π* transition at 400−470 and than the sizes of regular samples (Figure 4b). These results 575−675 nm, which ultimately lead to the more pronounced imply that the TmTPC-1@PVDF membrane can function as a photochromic behavior of TmTPC-1.55 UV imager and an X-ray sensor.

Table 1. Comparisons of Selected Unit Cell Parameters (a, b, c, and V) and π−π Interaction Distances of TmTPC-1 and TmTPC-2 before and after Irradiations

TmTPC-1 TmTPC-2 before UV after UV before X-ray after X-ray before UV after UV before X-ray after X-ray a (Å) 8.8508(16) 8.8436(14) 8.8631(4) 8.8491(4) 17.9171(6) 17.9251(13) 17.9101(7) 17.9182(8) b (Å) 37.001(5) 36.972(5) 36.9985(14) 36.9838(16) 9.4355(3) 9.4357(6) 9.4336(3) 9.4384(4) c (Å) 9.4346(17) 9.4214(15) 9.4245(4) 9.4145(4) 11.8787(4) 11.8884(9) 11.8747(4) 11.8800(5) V (Å3) 2964.1(9) 2957.9(8) 2966.6(2) 2958.1(2) 1641.43(10) 1644.0(2) 1639.95(10) 1642.44(12) dπ−π (Å) of 3.495 3.483 3.489 3.475 N/A N/A N/A N/A TPCdecorating dπ−π (Å) of 3.584 3.577 3.583 3.579 3.504 3.506 3.500 3.504 TPCbridging

2748 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

Tm. The phase purities of two complexes were confirmed by PXRD analyses as shown in Figure S1. Polyvinylidene Fluoride (PVDF) Membrane Fabrication. TmTPC-1 powder (120 mg) was sufficiently ground and mixed with 200 mg of PVDF in a mortar. After the addition of 2 mL of DMF, the mixture was transferred into a glass vial and treated with ultrasonification to make the powder evenly dispersed in the solution. The liquid mixture was then poured onto a glass plate and heated at 100 °C for 30 min in an oven. After the solvent was completely evaporated, the membrane was peeled off from the glass plate. The thickness of the membrane could be controlled by the loading ratio between TmTPC-1 and PVDF. Characterizations. Single-crystal X-ray diffraction measurements were performed using a Bruker D8-Venture single-crystal X-ray diffractometer. The diffraction data were collected using a Turbo X- ray Source (Mo Kα radiation, λ = 0.71073 Å) and a CMOS detector under room temperature. The data frames were collected using the program APEX3 and processed using the program SAINT routine in APEX3.62 The structures were solved by a direct method and refined on F2 by full-matrix least-squares methods using the SHELXTL-2014 program. Powder X-ray diffraction (PXRD) data were collected from Figure 4. (a) An illustration of TmTPC-1@PVDF membrane as a 5to50° with a step of 0.02° and the time for data collection was 0.15 UV radiation imager. (b) An illustration of TmTPC-1@PVDF s on a Bruker D8 Advance diffractometer with Cu Kα radiation (λ = membrane as a radiation indicator for X-ray beam alignment. 1.54056 Å) and a Lynxeye One-Dimensional detector. The IR spectra of complexes were recorded in the range of 400−4000 cm−1 using a Thermo Nicolet 6700 FTIR spectrometer equipped with a diamond fl ■ CONCLUSIONS attenuated total re ectance (ATR) accessory. The single-crystal solid- state UV−vis absorption spectra were recorded on a Craic In summary, we successfully developed two novel thulium Technologies microspectrophotometer. Crystals were placed on a terpyridine-carboxylate complexes, TmTPC-1 and TmTPC-2, quartz slide, and data were collected after autoset optimization. which are composed of similar components, but display Scanning electron microscopy (SEM) images and energy-dispersive distinct structures and remarkably different photoresponses. spectroscopy (EDS) analysis data were collected on a Zeiss Merlin TmTPC-1 possesses reversible photochromic transformation Compact LEO 1530 VP scanning electron microscope with the from colorless to green upon UV and X-ray irradiations, while energy of the electron beam being 15 kV. Crystals were mounted directly on the carbon conductive tape and the spectra acquisition TmTPC-2 exhibits unnoticeable color change under similar time was 60 s. The electron paramagnetic resonance (EPR) conditions. Complementary techniques including SCXRD, measurements were performed on a JEOL-FA200 spectrometer at EPR, PXRD, and FTIR revealed that the UV and X-ray the X-band with 100 kHz field modulation. The EPR spectra of induced photochromism of TmTPC-1 can be attributed to nonirradiated and irradiated samples were recorded at room enhanced intermolecular π−π interactions of dangling temperature and the microwave power used was 1.0 mW. decorating TPC units upon irradiation, which offer a more Thermogravimetric analysis (TGA) was carried out on a NETZSCH accessible intermolecular electron-transfer (IeMCT) pathway STA 449 F3 Jupiter instrument in the range of 30−800 °C under a •− nitrogen flow at a heating rate of 10 °C/min. High-dose X-ray to form TPC radicals compared to that of TmTPC-2. α Furthermore, TmTPC-1 can function as UV and X-ray irradiation experiments were conducted using a Cu K radiation fi source at a dose rate of 120 Gy/min and X-RAD SmART equipped dosimeters and be fabricated into a thin lm for imaging or with a W Kα radiation source at a dose rate of 26.5 Gy/min. radiation detection. The elucidation of structure−property correlation in this work sheds light on the future development ■ ASSOCIATED CONTENT of novel photoresponsive sensors. *sı Supporting Information ■ EXPERIMENTAL SECTION The Supporting Information is available free of charge at · ′ https://pubs.acs.org/doi/10.1021/acsami.0c20036. Reagents. Tm(NO3)3 6H2O (99.99%, Aladdin), N,N -dimethyl- formamide (DMF, 99%, Adamas), HCl (AR, 36−38%, Sinopharm PXRD patterns, SEM-EDS, UV−vis spectra, crystal ′ ′ ′′ ′ Chemistry Reagent Co., Ltd.), and 2,2 :6 ,2 -terpyridine-4 -carbox- images, FTIR spectra, TGA data, crystallographic data, ylic acid (HTPC) (Jilin Chinese Academy of Sciences - Yanshen and selected bond distances (PDF) Technology Co., Ltd.) were used as received from commercial suppliers without further purification. Crystallographic data for TmTPC-1 and TmTPC-2 · Synthesis of TmTPC-1 and TmTPC-2. Mixtures of Tm(NO3)3 (CIF) μ 6H2O (23.1 mg, 0.05 mmol), concentrated HCl (100 L), HTPC (13.8 mg, 0.05 mmol), DMF (1 mL), and deionized water (1 mL) were loaded into a 5 mL vial. The vial was then sealed and heated to ■ AUTHOR INFORMATION 100 °C for 24 h and cooled to room temperature under ambient Corresponding Author conditions. Colorless block crystals of TmTPC-2 were isolated after Jian Lin − Shanghai Institute of Applied Physics, Chinese being washed with deionized water and allowed to air-dry at room Academy of Sciences, Shanghai 201800, China; Key temperature. The synthetic method of TmTPC-1 is similar to that of TmTPC-2 except that hydrochloric acid was not added. The pH Laboratory of Interfacial Physics and Technology, Chinese values before and after the reactions are 3.11 and 5.30 for TmTPC-1, Academy of Sciences, Shanghai 201800, China; University of respectively. Those of TmTPC-2 before and after the reactions are Chinese Academy of Sciences, Beijing 100049, China; 0.69 and 4.43, respectively. The yields of TmTPC-1 and TmTPC-2 orcid.org/0000-0002-3536-220X; Email: linjian@ were calculated to be 100% and 74.89%, respectively, on the basis of sinap.ac.cn

2749 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 Authors ■ ACKNOWLEDGMENTS − Huangjie Lu Shanghai Institute of Applied Physics, Chinese This work was supported by the National Natural Science Academy of Sciences, Shanghai 201800, China; Key Foundation of China (21876182, 22076196, 21701184, and Laboratory of Interfacial Physics and Technology, Chinese 21906163), the Strategic Priority Research Program of the Academy of Sciences, Shanghai 201800, China; University of Chinese Academy of Sciences (XDA21000000), and the K.C. Chinese Academy of Sciences, Beijing 100049, China Wong Education Foundation (GJTD-2018-10). We thank the Zhaofa Zheng − Shanghai Institute of Applied Physics, members of the beamline BL14W1 at Shanghai Synchrotron Chinese Academy of Sciences, Shanghai 201800, China; Key Radiation Facility (SSRF) for the radiation indicator study. Laboratory of Interfacial Physics and Technology, Chinese Academy of Sciences, Shanghai 201800, China; University of Chinese Academy of Sciences, Beijing 100049, China ■ REFERENCES Zi-Jian Li − Shanghai Institute of Applied Physics, Chinese (1) Song, K.; Mohseni, M.; Taghipour, F. Application of Ultraviolet Academy of Sciences, Shanghai 201800, China; Key Light-Emitting Diodes (UV-LEDs) for Water Disinfection: A Review. Laboratory of Interfacial Physics and Technology, Chinese Water Res. 2016, 94, 341−349. Academy of Sciences, Shanghai 201800, China; University of (2) Decker, C. Kinetic Study and New Applications of UV Radiation Chinese Academy of Sciences, Beijing 100049, China; Curing. Macromol. Rapid Commun. 2002, 23, 1067−1093. orcid.org/0000-0002-3887-0234 (3)Suortti,P.;Thomlinson,W.MedicalApplicationsof − Hongliang Bao − Shanghai Institute of Applied Physics, Synchrotron Radiation. Phys. Med. Biol. 2003, 48,R1 R35. 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