Photoswitching of Local (Anti)Aromaticity in Biphenylene-Based Diarylethene Molecular Switches

Kalapos, Péter Pál; Mayer, Péter J.; Gazdag, Tamás; Demeter, Attila; Oruganti, Baswanth; Durbeej, Bo; London, Gábor

doi:10.1021/acs.joc.2c00504

Cited by 12 publications

(29 citation statements)

References 83 publications

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“…In many studies on photoswitchable diarylethenes, the formation of DDA was considered as a highly undesired side process that limits the number of common switches between the DAE-o and DAE-c isomers. [32][33][34][35][36][37][38][39] However, DDA dyes and their formation are very interesting and potentially useful compounds and reactions, respectively. In this review, we collected and analyzed all existing information on this subject.…”

Section: Introductionmentioning

confidence: 99%

Light‐Induced Dyotropic Rearrangement of Diarylethenes: Scope, Mechanism, and Prospects

Lvov

Kouame

Khusniyarov

2023

Chemistry A European J

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Irreversible two‐photon photorearrangement of 1,2‐diarylethenes is a unique process providing access to complex 2a1,5a‐dihydro‐5,6‐dithiaacenaphthylene (DDA) heterocyclic core. This reaction was serendipitously discovered during studies on photoswitchable diarylethenes and was initially considered as a highly undesired process. However, in recent years, it has been recognized as an efficient photochemical reaction, interesting by itself and as a promising synthetic method for the synthesis of challenging molecules. Herein, we discuss the state‐of‐the‐art in studies on this notable process.

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Section: Introductionmentioning

confidence: 99%

Light‐Induced Dyotropic Rearrangement of Diarylethenes: Scope, Mechanism, and Prospects

Lvov

Kouame

Khusniyarov

2023

Chemistry A European J

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“…[18][19][20][21][22][23][24] As an alternative for the synthesis of individual molecules, the control of optoelectronic properties of BP has been realized recently by combining it with dithienylethene-type molecular switches. [25] Although complex organic synthesis of unique molecules remains the most important tool for the development of organic functional and smart materials, the investigation of donor-acceptor molecular complexes provides a fruitful approach for tuning structure and properties of organic materials. [26] These complexes with relatively simple components became relevant in the fields or organic electronics, [27 -31] crystal engineering, [32 -34] smart materials [35] and sensors.…”

Section: Introductionmentioning

confidence: 99%

“…Synthetic approaches are available for the systematic investigation of structure‐property relationships through the preparation of various BP derivatives [18–24] . As an alternative for the synthesis of individual molecules, the control of optoelectronic properties of BP has been realized recently by combining it with dithienylethene‐type molecular switches [25] …”

Section: Introductionmentioning

confidence: 99%

The π‐Molecular Complex of Biphenylene and Tetracyanoethylene

Dobszay,

Mayer,

Holczbauer

et al. 2023

Helvetica Chimica Acta

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The investigation of the biphenylene (BP)‐tetracyanoethylene (TCNE) π‐molecular complex is reported. The first study on this complex appeared in 1961 and was considered as a charge transfer complex with a symmetric, co‐planar arrangement of the components. Moreover, it was assumed that this arrangement is not only dictated by the formation of a Mulliken‐type donor‐acceptor complex, but also by the electronic stabilization of the “cyclobutadieneoid” central ring of biphenylene through complex formation. Yet, crystal structure and associated computational analysis have not verified these predictions so far. We found that factors other than charge‐transfer interactions are most influential in the crystal formation. The low association constant in solution, and the weak interaction between the components in the 1:1 crystal structure point towards the low contribution of charge transfer interactions to their binding. Nevertheless, the presence of these interaction is hinted by the color of its solution and verified by theoretical calculations. Furthermore, Nucleus Independent Chemical Shift (NICS) calculations were carried out to characterize potential changes in the (anti)aromatic character of BP upon complex formation. The NICS(0) values of the rings of BP exhibit tiny changes both in the BP‐TCNE dimer and in the crystal, which also suggests weak electronic interactions between them.

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“…[27] The photocyclization driven by excited-state aromaticity and antiaromaticity was also reported by Durbeej and co-workers. [28,29] Beside these previous attempts, the usage of non-planar aromatic units remains still challenging. The effect of aromatic stabilization for the open-form isomer may be strongly perturbed.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Photochromic Properties of Diaryl [5]Helicene Derivatives

Li,

Fang,

Chen

et al. 2023

Chemistry A European J

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Photoinduced tuning of aromaticity and correlative molecular properties has attracted enormous interest in recent years for both modulating photochromism properties and designing novel photochromic materials. Here, we report on the synthesis and photochemical characterizations investigation of diaryl[5]helicene based diarylethene molecular switches. 3,4‐Bis(2,4‐dimethyl‐5‐phenylthiophen‐3‐yl)dibenzo[c,g]phenanthrene derivative 1a showed no photochromic reaction, while 3,4‐bis(2‐methyl‐5‐phenylthiophen‐3‐yl)dibenzo[c,g]phenanthrene derivative 2a and 3,4‐bis(5‐methyl‐2‐phenylthiazol‐4‐yl)dibenzo[c,g]phenanthrene derivative 3a exhibited reversible photochromism in different aprotic solvents with specific light irradiation. Meanwhile, the diarylethene compounds 2a and 3a underwent turn‐off mode fluorescence photoswitchings together with the photoisomerization reaction upon light irradiation. Remarkably, the photoinduced changes in aromaticity of [5]helicene as a central ethene bridge along with the relative smaller activation energy and higher frequency factor facilitated the thermal bleaching rates of diarylethene switches 2 and 3 in solution. This research provides a new insight for designing aromatic diarylethene photoswitches for reversible fluorescence switching behaviour, photoinduced changes in aromaticity and further fast thermal back reaction.

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Photoswitching of Local (Anti)Aromaticity in Biphenylene-Based Diarylethene Molecular Switches

Cited by 12 publications

References 83 publications

Light‐Induced Dyotropic Rearrangement of Diarylethenes: Scope, Mechanism, and Prospects

Light‐Induced Dyotropic Rearrangement of Diarylethenes: Scope, Mechanism, and Prospects

The π‐Molecular Complex of Biphenylene and Tetracyanoethylene

Synthesis and Photochromic Properties of Diaryl [5]Helicene Derivatives

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