Photoresponsive gadolinium–anthracene complexes: tuning the orientation and π–π stacking of anthracene groups<i>via</i>alkyl ester substituents of phosphonate ligands

Huang, Xingyuan; Sun, Guobin; Chen, Yiqing; Wen, Ge-Hua; Bao, Song‐Song; Zheng, Li‐Min

doi:10.1039/d2ce01012g

Cited by 2 publications

(3 citation statements)

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“…The latter was found to be capable of affecting the orientation and stacking of anthracene groups in the lattice of a few mononuclear gadolinium complexes. 28 In this work, we report two new dysprosium complexes containing Dy 2 O 2 motifs and anthracene units, namely…”

Section: ■ Introductionmentioning

confidence: 97%

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Tuning the Single-Molecule Magnet and Photoluminescence Properties of Binuclear Dysprosium Complexes by Light

Huang

Zheng

2022

Crystal Growth & Design

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Lanthanide-based single-molecule magnets (Ln-SMMs) showing a synergistic magnetic and photoluminescence change in response to external stimuli are very attractive due to their potential applications in information storage, spintronics, and devices. In this paper, we report two dysprosium complexes c o n t a i n i n g D y 2 O 2 m o t i f s a n d a n t h r a c e n e u n i t s , n a m e l y [Dy 2 (SCN) (2), where HL stands for 2,6-dimethoxyphenol, dmpma is 9-dimethylphosphonomethylanthracene, and depma is 9-diethylphosphonomethylanthracene. Both exhibit slow magnetization relaxation at zero dc field, characteristic of SMM behavior. Interestingly, complex 2 shows two thermally activated relaxation processes, attributed to the presence of disordered anthracene groups. The effective energy barriers are 117.7 K for 1 and 48.4 and 110.8 K for 2. Under 395 nm UV light irradiation, compounds 1 and 2 undergo a [4 + 4] photocycloaddition reaction to form [Dy 2 (SCN) 4 (L) 2 (dmpma 2 )(H 2 O) 2 ] n (1UV) and [Dy 2 (SCN) 4 (L) 2 (depma 2 )(H 2 O) 2 ] n •nH 2 O (2UV) with linear chain structures, where the structural transformation of complex 2 occurs in a single-crystal-to-single-crystal (SC-SC) fashion. Synergistic changes in photoluminescence and SMM behavior were observed for both compounds before and after light irradiation. The results show that the photodimerization of anthracene groups not only inhibits the magnetic relaxation in 1 and 2 and increases the magnetization reversal barrier (172.0 K for 1UV, 120.5 K for 2UV) but also eliminates the anthracene group disorder in compound 2, leading to a significant change in the magnetic dynamics from a dual-relaxation to a single-relaxation process.

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Section: ■ Introductionmentioning

confidence: 97%

“…Among the various approaches to achieve this goal, one effective method is to modify the 2,6-dimethoxyphenol ligand and/or change the alkyl ester substituent of the phosphonate ligand. The latter was found to be capable of affecting the orientation and stacking of anthracene groups in the lattice of a few mononuclear gadolinium complexes …”

Section: Introductionmentioning

confidence: 99%

Tuning the Single-Molecule Magnet and Photoluminescence Properties of Binuclear Dysprosium Complexes by Light

Huang

Zheng

2022

Crystal Growth & Design

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“…Photochromic smart molecules, as one of the famous multifunctional materials, have been widely used in optical switch, information storage, sensor, and other fields. − They can show color changes under light irradiation with reversible changes in physicochemical properties (such as luminescence, − magnetism, − , and conductivity − ). So far, the metal–organic hybrid photochromic family has increased the possibilities for integrating the merits of inorganic and organic units at the molecular scale, providing a platform for researchers to design and create novel photochromic materials with diverse photoresponsive functionalities. − Especially, electron-transfer (ET) photochromic complexes containing viologen ligands and their derivatives have attracted extensive attention. − However, works on this photochromic system constructed by new photoactive ligands are still challenging due to the difficulty of synthesis and serendipity of photochromism.…”

Section: Introductionmentioning

confidence: 99%

Photochromism and Photomagnetism in Two Ni(II) Complexes Based on a Photoactive 2,4,6-Tris-2-Pyridyl-1,3,5-Triazine Ligand

Li,

Wang,

Han

et al. 2024

Inorg. Chem.

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It is still challenging to construct novel photochromic and photomagnetic materials in the field of molecular materials. Herein, the 2,4,6-tris-2-pyridyl-1,3,5-triazine (TPTz) molecule was found to display photochromic properties under room temperature light irradiation. Two mononuclear structures,were obtained by assembling TPTz with polydentate O-ligands (oxalate and phosphonate) and the paramagnetic Ni 2+ ions. The electrontransfer (ET)-dominated photochromism was observable in 1 and 2 after light irradiation with the photogeneration of relatively stable radicals, and the resultant photochromism was demonstrated via UV−vis, photoluminescence, X-ray photoelectron spectra, electron paramagnetic resonance spectra, and molecular orbital calculations. Due to the denser stacking interactions between the adjacent organic molecules, 2 exhibited a faster photochromic rate than 1. Compared with 1 and 2, compound 3 did not show photochromic behavior, which was deciphered by the theoretical calculations for all of the compounds. Importantly, the magnetic couplings appeared between photogenerated radicals and paramagnetic Ni 2+ ions, resulting in a scarcely photomagnetic phenomenon of 1 and 2 in the Ni-based electron transfer photochromic materials. This work enriches the available kind of ligands for the design of ET photochromic materials, putting forward a method to tune the electron transfer photochromic efficiency in the molecular materials.

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Photoresponsive gadolinium–anthracene complexes: tuning the orientation and π–π stacking of anthracene groupsviaalkyl ester substituents of phosphonate ligands

Abstract: Controlled assembly of metal-anthracene complexes is important for the development of smart photoresponsive materials based on [4+4] anthracene photocycloaddition reactions. Here, we report three mononuclear complexes containing two anthracene units,...

Cited by 2 publications

References 41 publications

Tuning the Single-Molecule Magnet and Photoluminescence Properties of Binuclear Dysprosium Complexes by Light

Tuning the Single-Molecule Magnet and Photoluminescence Properties of Binuclear Dysprosium Complexes by Light

Photochromism and Photomagnetism in Two Ni(II) Complexes Based on a Photoactive 2,4,6-Tris-2-Pyridyl-1,3,5-Triazine Ligand

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