Photochromic and electrochromic properties of a viologen-based multifunctional Cd-MOF

Li, Haiyang; Hua, Xue; Fu, Ting; Liu, Xiaofei; Zang, Shuang‐Quan

doi:10.1039/d2cc02703h

Cited by 29 publications

(21 citation statements)

References 59 publications

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“…To further study this photochromic phenomenon, the solid-state UV–vis absorbance spectra were acquired on crystal powders of 1 and 2 using a TU-1901 ultraviolet spectrometer. Before UV light irradiation, a strong absorption band at around 230–350 nm was observed in 1 and 2 , which should be attributed to the π–π* transition of the CV ligands . For 1 , a new electron absorption band centered at 652 nm appeared on exposure to UV light (365 nm, ca.…”

Section: Resultsmentioning

confidence: 99%

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Selective Photochromic Response to Low-Dose X-ray Radiation Detection in One-Dimensional Cadmium-Viologen Complexes

Shen

et al. 2023

Inorg. Chem.

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Photochromic viologen-based materials have emerged as one of the most promising candidates for the development of X-ray light detection applications, including medical diagnosis and treatment, environmental radiation inspection, and industrial crack detection. However, the design and construction of low-dose X-ray-sensitive complexes remains an immense challenge, especially for the in-depth dissection of their response mechanisms. Herein, by using N,N′-4,4′-bipyridiniodipropionate (CV) as functional sensitive structural units and cadmium as heavy atoms, two cadmium-viologen complexes with one-dimensional chained structures, namely, [Cd2Cl4(CV)(H2O)2] n (1) and [CdBr2(CV)] n (2), have been constructed, which exhibit a remarkable and selective photochromic response to low-dose X-ray radiation detection. Compound 1 is visually sensitive to both X-ray and UV light due to the more accessible photoinduced electron transfer (ET) pathways, while compound 2 only shows a slight color-changing process in response to UV light, in conformity with UV–vis absorbance analyses and kinetic studies. Surprisingly, compound 2 has longer ET pathways than 1, but not in response to high-energy X-ray light, seeming to contradict the previous phenomena. On further analysis, the key point in achieving X-ray-sensitive behavior should be a good balance among the electron donor–acceptor distance, intermolecular interaction, and X-ray absorbing capacity, as verified by density functional theory (DFT) and X-ray absorption strength calculations, X-ray photoelectron spectra, electron paramagnetic resonance measurements, and independent gradient model analysis. In particular, compound 1 is unprecedentedly sensitive to soft X-ray radiation, accompanied by an X-ray detection limit of as low as 2.91 Gy. These findings push forward the further development of low-dose X-ray sensing materials.

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Section: Resultsmentioning

confidence: 99%

“…Before UV light irradiation, a strong absorption band at around 230−350 nm was observed in 1 and 2, which should be attributed to the π−π* transition of the CV ligands. 40 For 1, a new electron absorption band centered at 652 nm appeared on exposure to UV light (365 nm, ca. 90 mW/ cm 2 ) for 5 s at RT in air (Figure 2a).…”

Section: Photochromic Propertiesmentioning

confidence: 99%

Selective Photochromic Response to Low-Dose X-ray Radiation Detection in One-Dimensional Cadmium-Viologen Complexes

Shen

et al. 2023

Inorg. Chem.

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“…Nowadays POM-viologen hybrid crystalline photochromic materials combining multiple color-changing capabilities and exploring multifunction applications have become a research hotspot. [98][99][100][101][102][103] For example, Guo et al successfully prepared a new two-dimensional hybrid material EV[Mo 9 O 28 ] (EV 2+ = ethyl viologen cation) by introducing the ethyl viologen, a wellknown electron acceptor, into the polyoxomolybdate layered structure. 98 As shown in Fig.…”

Section: Viologen Exists As Counter Cationmentioning

confidence: 99%

Recent progress in polyoxometalate–viologen photochromic hybrids: structural design, photochromic mechanism, and applications

Yang-Tao

Yang

et al. 2023

Inorg. Chem. Front.

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“…However, there is no significant color change under irradiation at 520 and 660 nm. The photochromism upon 405 nm light irradiation is confirmed by UV/Vis absorption, in which two new broad absorption peaks appear in the visible region at 630 nm and 745 nm similar to those of viologen compounds [23,24] . And these absorption bands gradually rise upon increasing exposure time (Figure 2b and Figure 2c), and keep nearly unchanged at 300 s. The PXRD and IR spectra after irradiation (Figures S5–S6) are essentially identical to the original ones, meaning the consistency of the main structures between the two states.…”

Section: Resultsmentioning

confidence: 83%

Photo Responsive Electron and Proton Conductivity within a Hydrogen‐Bonded Organic Framework

et al. 2023

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Rational design of crystalline porous materials with coupled proton‐electron transfer has not yet been reported to date. Herein, we report a donor‐acceptor (D‐A) π‐π stacking hydrogen‐bonded organic framework (HOF; HOF‐FJU‐36) with zwitterionic 1,1′‐bis(3‐carboxybenzyl)‐4,4′‐bipyridinium (H2L2+) as acceptor and 2,7‐naphthalene disulfonate (NDS2−) as donor to form a two‐dimensional (2D) layer. Three water molecules were situated in the channels to connect with acidic species through hydrogen bonding interactions to give a 3D framework. The continuous π‐π interactions along the a axis and the smooth H‐bonding chain along the b axis provide the electron and proton transfer pathways, respectively. After 405 nm light irradiation, the photogenerated radicals could simultaneously endow HOF‐FJU‐36 with photoswitchable electron and proton conductivity due to coupled electron‐proton transfer. By single‐crystal X‐ray diffraction (SCXRD) analyses, X‐ray photoelectron spectroscopy (XPS), transient absorption spectra and density functional theory (DFT) calculations, the mechanism of the switchable conductivity upon irradiation has been demonstrated.

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Photochromic and electrochromic properties of a viologen-based multifunctional Cd-MOF

Abstract: A pair of novel multifunctional MOFs material [Cd2(L)2(D/L-Lm) ·(H2O)2] ·5H2O have been synthesized by combining viologen-functionalized ligand H2L+·Cl- and chiral D/L-tartaric acid (H2Lm) with a simple solvent thermal method. Due...

Cited by 29 publications

References 59 publications

Selective Photochromic Response to Low-Dose X-ray Radiation Detection in One-Dimensional Cadmium-Viologen Complexes

Selective Photochromic Response to Low-Dose X-ray Radiation Detection in One-Dimensional Cadmium-Viologen Complexes

Recent progress in polyoxometalate–viologen photochromic hybrids: structural design, photochromic mechanism, and applications

Photo Responsive Electron and Proton Conductivity within a Hydrogen‐Bonded Organic Framework

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