A series of host–guest coordination polymers containing viologens: syntheses, crystal structures, thermo/photochromism and factors influencing their thermo/photochromic behaviors

Kan, Wei-Qiu; He, Yuan‐Chun; Wen, Shi-Zheng; Zhao, Pusu

doi:10.1039/c9dt03929e

Cited by 50 publications

(28 citation statements)

References 55 publications

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“…As is known, high temperature facilitates charge recombination . For the reported thermally induced electron transfer coordination compounds, thermochromism occurs between 90 and 160 °C, ,,− while complex 1 could undergo thermochromic behavior at 180 °C. It is also worth noting that 1Q is a very stable electron transfer system under oxygen-rich atmosphere.…”

Section: Resultsmentioning

confidence: 97%

A Multistimuli Responsive Crystalline Cd(II)-Viologen Coordination Polymer with Single-Crystal–Single-Crystal Transformation

et al. 2021

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It is necessary to develop stable and fast multistimuli responsive materials due to the growing demand in our daily life. In this work, a new viologen-based Cd-complex (1) exhibits multiple thermochromic and photochromic behaviors through 10 states with 7 colors. For example, it responds to both Cu Kα/Mo Kα X-ray sources and UV dual light quickly with a color change from colorless to dark blue (1X) (Cu Kα/Mo Kα X-ray sources) and cyan (1-UV) (UV light), respectively. Interestingly, it exhibits a three-step coloration phenomenon when heated, which is unprecedented in viologen compounds. Crystal 1 undergoes a color change to pink, blue, and brown under 130, 180, and 240 °C, respectively. In addition, upon fumigation, both 1P and 1Q undergo a decoloration process to colorless (1K) and yellow (1T), respectively. Four more states (1P, 1K, 1T, and 1O) obtained via dehydration–hydration treatment are all photochromic. More importantly, via single-crystal–single-crystal transformation (SC–SC), the photochromic and thermochromic behaviors of 1 were investigated from the molecular level, which is also rather rare for thermochromic species. The detailed electron donor and the pathways for electron transfer were clearly given according to the results of crystal structure. The colorful states upon external stimuli may be attributed to the multiple pathways for electron transfer.

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Section: Resultsmentioning

confidence: 97%

A Multistimuli Responsive Crystalline Cd(II)-Viologen Coordination Polymer with Single-Crystal–Single-Crystal Transformation

et al. 2021

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“…Driven by the need to develop technologically smart materials for use in a variety of areas, including sensing, nanotechnology, coating, catalysis, optical switches, data storage, and controlled drug delivery vehicles, a number of stimuli-responsive materials have been successfully developed so far. − Among the stimuli-responsive materials, the chromic materials are vigorously sought-after for easily gathering information about the changing environment because color changes discerned with the naked eye can be connected to the chemical or physical stimuli. − In the past two decades, there has been an upsurge in the study of electron-transfer chromic materials due to their high chromic performances, which can exhibit reversible color changes upon external stimuli. − Viologen-based coordination polymers are typical electron-transfer chromic materials that can exhibit three oxidation states: neutral state, radical cation state, and divalent cation state. − The color change from divalent cation state to monovalent cation state is easily observed, but it is difficult to achieve multichromism for viologen-based materials . Recently, to enrich the chromic family, extended viologen-based coordination polymers with chromic performance have been successfully synthesized and provide new opportunities to obtain cost-effective chromic materials. − However, coordination polymers with extended viologen ligands are still quite limited, and the construction of such prominent materials with high chromic performance remains challenging.…”

Section: Introductionmentioning

confidence: 99%

Tri(pyridinyl)pyridine Viologen-Based Kagome Dual Coordination Polymer with Selective Chromic Response to Soft X-ray and Volatile Organic Amines

Zhang

et al. 2020

Inorg. Chem.

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The development of new responsive smart materials has been highly desirable in the recent decade due to growing demand in our daily life, and extended viologen-based coordination polymers are regarded as proper and promising candidates for stimuli-responsive study. A tri(pyridinyl)pyridine viologen-based Kagome dual (kgd) topological coordination polymer, [Mn 3 Cl 4 (tpptb) 2 ]•Cl 2 •(H 2 O) 2 , (tpptb = N,N′,N″-tri(3-carboxybenzyl)-2,4,6-tri(pyridinium-4-yl)pyridine; 1) has been solvothermally synthesized, which can selectively respond to soft X-ray Al−Kα (λ = 8.357 Å) irradiation but not to UV light and hard X-rays of λ < 1.5418 Å at room temperature. Appealingly, 1 is very sensitive and convenient for the visual detection of various volatile amine vapors, especially ethylamine vapors at a low concentration of 100 ppm, and the vapochromic sample can be recovered after exposure in the air at room temperature. The sequence of amines in vapochromism could be rationalized by combined consideration of vapor pressure, the molecular size, and electron-donor ability of various amine molecules as well as the void spaces of 1. In addition, 1 exhibits an obvious hydrochromic transformation upon heating in the air and an anhydrous atmosphere. Combined XPS and EPR confirmed that these physical and chemical stimuli can cause electron transfer from electron-rich groups to quaternary nitrogen atoms of the ligand to generate chargeseparated radicals, leading to soft X-ray-induced photochromic and selective vapochromic behavior of 1. Such behavior indicates that it will become a convenient, recyclable, and practical multifunctional material for chemical and environmental sensing. These results provide an effective avenue for the rational design and synthesis of multifunctional chromic materials for potential use in sensing devices.

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“…These may be attributed to the formation of viologen radicals through photo-induced chromism generated by single-electron transfer. 47,48 It is well known that viologen-based materials are electrically sensitive and have reversible electrochromic properties. 49 To further explore the electrochemical characteristics of the materials, cyclic voltammetry (CV) of D-Cd-MOF was performed in 0.5 M LiClO 4 solution via a three-electrode system, wherein the material deposited on FTO glass was used as the working electrode, Pt foil as the counter electrode, and a Ag/AgCl electrode as the reference.…”

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confidence: 99%

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

Hua

et al. 2022

Chem. Commun.

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A series of host–guest coordination polymers containing viologens: syntheses, crystal structures, thermo/photochromism and factors influencing their thermo/photochromic behaviors

Abstract: Some viologen-containing compounds displaying thermo/photochromic behaviors which can be used as inkless print media and anti-counterfeiting materials have been reported.

Cited by 50 publications

References 55 publications

A Multistimuli Responsive Crystalline Cd(II)-Viologen Coordination Polymer with Single-Crystal–Single-Crystal Transformation

A Multistimuli Responsive Crystalline Cd(II)-Viologen Coordination Polymer with Single-Crystal–Single-Crystal Transformation

Tri(pyridinyl)pyridine Viologen-Based Kagome Dual Coordination Polymer with Selective Chromic Response to Soft X-ray and Volatile Organic Amines

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

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