Elsevier

Dyes and Pigments

Volume 176, May 2020, 108202
Dyes and Pigments

Synthesis and characterization of gated photochromic diarylethene functionalized with dipicolylamine

https://doi.org/10.1016/j.dyepig.2020.108202Get rights and content

Highlights

  • Cu2+ ion gated photochromic diarylethene functionalized with dipicolylamine have been synthesized and investigated.

  • The photo-cyclization reaction was significantly suppressed in dipicolylamine containing BTF6 moiety.

  • The reversible gated photochemical reactivity was achieved by the alternating addition of Cu2+ and EDTA.

Abstract

1,2-bis(2-methyl-1-benzothiophene-3-yl)perfluorocyclopentene (BTF6) based photochromic diarylethene functionalized with dipicolylamine (DPA), BTF-DPA has been synthesized, and its photochromic properties have been determined. The photoconversion reaction of o-BTF-DPA was prohibited due to the electronic effect originated from electron donation from DPA to the diarylethene BTF6 framework. The addition of Cu2+ gave rise to dramatically increase the conversion yield of o-BTF-DPA from 0 to 23.86% (for o-BTF-DPA-Cu2+) due to diminishing the electron donation ability of DPA. The addition of EDTA removed Cu2+ from BTF-DPA-Cu2+, which result in suppressing the conversion yield o-BTF-DPA. We also synthesized BTF-DMA and BTF-TMA to examine the mechanism of gated photochromism in diarylethenes. We found that the electron donation ability of DPA plays a critical role in the modulation of photochromic reactivity. The results demonstrated that BTF-DPA could be applicable as a “molecular lock” that requires Cu2+ “key” and EDTA “hand” to unlatch the key. We believe this strategy can be further extended to develop the gated photochromic systems by controlling the electronic state via non-bonding nitrogen-containing ligands.

Introduction

Photochromic materials can undergo reversible photoisomerization, which enables them for possible applications including molecular switches [[1], [2], [3], [4], [5], [6], [7], [8], [9]], optical memory devices [[6], [7], [8], [9], [10]], molecular logic devices [[11], [12], [13], [14], [15]], and gas adsorption [16]. Among the photochromic materials, fluorinated diarylethene derivatives have been received increasing attention owing to their excellent fatigue resistance and thermal stability [1,9,[17], [18], [19], [20], [21], [22], [23], [24], [25]]. Ideal photochromic materials with broad applicability for molecular optical memory devices and logic gates should have multiple optical states [13,[26], [27], [28]]. Despite the promising gated photochromism in memory and data manipulation applications [29,30], limited gated photochromic systems have been examined. Several examples have been reported to develop the gated photochromic diarylethenes systems, such as selective oxidization/reduction [30], complexation to metal ions [26,[31], [32], [33]], the saccharides [34], BF3 [29,[35], [36], [37]], acid/base gating systems [4,15,[38], [39], [40], [41]], and the formation of hydrogen bonds. Besides, Diels-Alder [42], esterification [43], phosphorylating reactions [44] based gated photochromism have been examined. However, previous approaches are ultimately limiting due to the lack of a simple route to develop the gated photo-reactivity. Therefore there are obstacles to extend these strategies to develop different gating photochromic systems.

In our previous study, we proposed that the gated photochromic materials could be developed through the rational design of the electronic states of 1,2-bis(2-methyl-1-benzothiophene-3-yl)perfluorocyclopentene (BTF6). To realize this hypothesis, we have developed an azadithiacrown-ether (AE) functionalized BTF6, BTF-AE, where the AE ring was appended to the BTF6 framework through a styryl linker [33]. We demonstrated the photochromic reactivity could be controlled by the existence of Ag+ ion, where the existence of Ag+ ion can change the electronic state of BTF-AE. Dipicolylamine (DPA) has been widely adopted to develop the metal ions sensors, especially for zinc and copper ions [[45], [46], [47], [48], [49], [50]]. Upon binding with metal ion, the excited state energy level of DPA functionalized fluorophore decreased, which leads to a blue shift in the absorption spectrum.

In the present study, we report the synthesis and characterization of a novel DPA functionalized BTF6, BTF-DPA, to elucidate this hypothesis further. The DPA was appended to the BTF6 framework through a styryl linker. Surprisingly, the photochromic reactivity of BTF-DPA was significantly decreased by conjugating the DPA ligand to the BTF6 frame. On the other hand, the addition of Cu2+ ion activated the diminished photochromic reactivity of BTF-DPA by the formation of complex BTF-DPA-Cu2+. The photochromic reactivity can be quenched again by removing Cu2+ ion with EDTA. We also synthesized BTF-DMA and BTF-TMA to examine the mechanism of gated photochromism of BTF6. We demonstrated that the photochromic reactivity of BTF6 could be controlled by introducing the non-bonding nitrogen-containing ligands. More importantly, this strategy can be extended to develop the gated photochromic materials by controlling the electronic state via non-bonding nitrogen-containing ligands.

Section snippets

Chemicals

All reagents and solvents for synthesis were reagent grade and purchased from TCI, Alfa Aesar, Sigma-Aldrich, Samchun and were used as received. Spectroscopic solvents for characterization were purchased from Sigma-Aldrich.

Experimental

High-performance liquid chromatography (HPLC) was obtained using a Young Lin SP-930D liquid chromatography coupled with a UV-730D detector. The 1H NMR and 13C NMR analysis were conducted on a JEOL JNM-AL300 spectrometer at 300 MHz and 75 MHz. High-resolution mass spectra

Synthesis of BTF-DPA, BTF-DMA, and BTF-TMA

The dipicolylamine functionalized diarylethene, BTF-DPA was synthesized using a conventional Wittig reaction with formylated diarylethene 7 [52] and phosphonium ylide reagent 4 formed from 4-[bis(pyridin-2-ylmethyl)amino]benzaldehyde [46] in 31% yield (Scheme 1). Reference compound BTF-DMA was also synthesized by a conventional Wittig reaction with formylated diarylethene 7 [52] and phosphonium ylide reagent 6 formed from 4-(dimethylamino)benzaldehyde in 84% yield (Scheme 1). BTF-TMA was

Conclusions

A novel dipicolylamine (DPA) functionalized BTF6, BTF-DPA, and its model compounds BTF-DMA and BTF-TMA have been synthesized and examined their photochromic properties. We have demonstrated that the photochromic reactivity of BTF6 can be controlled by introducing non-bonding nitrogen-containing DPA ligands. The locked photochromic activity of BTF-DPA was unlocked upon the addition of Cu2+. The photo-cyclization yield was dramatically increased from 0 (BTF-DPA) to 23.86% (BTF-DPA-Cu2+). The

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This subject is supported by Korea Ministry of Environment as “Environmental Health R&D Program” (2012001370010). This subject is supported by Nano R&D program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2016M3A7B4909776). This subject is supported by a grant from Kyung Hee University in 2015 (20150642).

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