Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

Azo-dimethylaminopyridine-functionalized Ni(II)-porphyrin as a photoswitchable nucleophilic catalyst

• Jannis Ludwig,
• Julian Helberg,
• Hendrik Zipse and
• Rainer Herges

Beilstein J. Org. Chem. 2020, 16, 2119–2126, doi:10.3762/bjoc.16.179

• following several approaches using a variety of photochromic systems. Feringa et al. recently published a review including systems based on double bond isomerizations [1]. An earlier review from the same group summarized light and redox responsive catalytic systems including azobenzenes, diarylethenes

• , spiropyranes, and stilbenes [2]. Diarylethenes were reported in the context of photoswitchable catalysis as inhibitors of the Karstedt´s catalyst [3] and for pKa modulation in acid–base-controlled processes [4]. Molecular motors for stereodivergent anion binding catalysis [5], azopeptides for the acetylation

Light-controllable dithienylethene-modified cyclic peptides: photoswitching the in vivo toxicity in zebrafish embryos

• Sergii Afonin,
• Oleg Babii,
• Aline Reuter,
• Volker Middel,
• Masanari Takamiya,
• Uwe Strähle,
• Igor V. Komarov and
• Anne S. Ulrich

Beilstein J. Org. Chem. 2020, 16, 39–49, doi:10.3762/bjoc.16.6

• in tissues. Among several known photoswitches [18] that are being used in peptides [19][20][21][22][23], diarylethenes (DAE) have increasingly attracted attention in recent years [22][23]. Photoswitchable DAE-derived molecules offer several advantages for medical applications, as their photoforms are

A combinatorial approach to improving the performance of azoarene photoswitches

• Joaquin Calbo,
• Aditya R. Thawani,
• Rosina S. L. Gibson,
• Andrew J. P. White and
• Matthew J. Fuchter

Beilstein J. Org. Chem. 2019, 15, 2753–2764, doi:10.3762/bjoc.15.266

• photopharmacology [1][2] and optochemical genetics [3] to data storage [4]. Numerous classes of photochromic molecules exist, each with their own unique characteristics. For example, spiropyrans [5][6] may exhibit significant changes in solubility upon photoswitching, whilst the photoswitching of diarylethenes [7

A toolbox of molecular photoswitches to modulate the CXCR3 chemokine receptor with light

• Xavier Gómez-Santacana,
• Sabrina M. de Munnik,
• Tamara A. M. Mocking,
• Niels J. Hauwert,
• Shanliang Sun,
• Prashanna Vijayachandran,
• Iwan J. P. de Esch,
• Henry F. Vischer,
• Maikel Wijtmans and
• Rob Leurs

Beilstein J. Org. Chem. 2019, 15, 2509–2523, doi:10.3762/bjoc.15.244

• the binding affinity for the target protein [3][4][5] or the intrinsic functional activity (efficacy) [6][7]. Despite the considerable number of photoswitches reported to date, such as spiropyrans, diarylethenes, fulgides or azobenzenes, the most widely used moiety in the photopharmacology is the

Ultrafast processes triggered by one- and two-photon excitation of a photochromic and luminescent hydrazone

• Alessandro Iagatti,
• Baihao Shao,
• Alberto Credi,
• Barbara Ventura,
• Ivan Aprahamian and
• Mariangela Di Donato

Beilstein J. Org. Chem. 2019, 15, 2438–2446, doi:10.3762/bjoc.15.236

• photoswitches have been developed and successfully employed in many technological fields [20][21][22][23]. Among others, azobenzenes [24], spiropyranes [25], diarylethenes [26] and their derivatives have been intensively applied. Despite the numerous successful applications of several synthetized switches, some

Photochromic diarylethene ligands featuring 2-(imidazol-2-yl)pyridine coordination site and their iron(II) complexes

• Andrey G. Lvov,
• Max Mörtel,
• Anton V. Yadykov,
• Frank W. Heinemann,
• Valerii Z. Shirinian and
• Marat M. Khusniyarov

Beilstein J. Org. Chem. 2019, 15, 2428–2437, doi:10.3762/bjoc.15.235

• ][3][4][5][6][7]. Reversible change of the electronic structure of diarylethene photochromes [8][9][10] upon photocyclization is a promising tool to control the electronic structure of coordinated metal ions and, consequently, associated properties. Thus, diarylethenes were integrated into well-known

• approach for achieving a strong impact of the photochromic reaction on the electronic structure of a coordinated metal ion. Previously reported examples of the second group ligands are collected in Figure 1. Yam et al. developed diarylethenes I [17] and II [18] and synthesized their rhenium(I) complexes

• . To meet these requirements, a new family of ligands VI based on the 2-(imidazol-2-yl)pyridine unit as a heteroaryl moiety and various ethene bridges is presented in this work. Diarylethenes with the 2-(imidazol-2-yl)pyridine being a part of the ethene bridge were previously developed [18][29] and

Mono- and bithiophene-substituted diarylethene photoswitches with emissive open or closed forms

• A. Lennart Schleper,
• Mariano L. Bossi,
• Vladimir N. Belov and
• Stefan W. Hell

Beilstein J. Org. Chem. 2019, 15, 2344–2354, doi:10.3762/bjoc.15.227

• open forms with rather low emission efficiency. The photoswitching kinetics was studied at several wavelengths with UV and visible light. New diarylethenes underwent ring-closure reactions by irradiation with UV light (365 nm, 405 nm), and the reversible ring-opening by irradiation with visible light

• large fluorescence quantum yield, compound SyOTh1 emerged as a candidate for single-molecule based super-resolution fluorescence microscopy. Keywords: diarylethenes; dyes; fluorescence; organic synthesis; photochromism; photoswitching; Introduction Reversibly photoswitchable diarylethenes (DAEs) with

• Table 1) is only weakly fluorescent (φFl ≈ 0.01) [4]. In general, diarylethenes with fluorescent open forms are rare, while photoswitchable compounds with highly fluorescent “open” and “closed” forms represent a yet unknown and unique class of ratiometric fluorophores. Recently, we demonstrated that

Aggregation-induced emission effect on turn-off fluorescent switching of a photochromic diarylethene

• Luna Kono,
• Yuma Nakagawa,
• Ayako Fujimoto,
• Ryo Nishimura,
• Yohei Hattori,
• Toshiki Mutai,
• Nobuhiro Yasuda,
• Kenichi Koizumi,
• Satoshi Yokojima,
• Shinichiro Nakamura and
• Kingo Uchida

Beilstein J. Org. Chem. 2019, 15, 2204–2212, doi:10.3762/bjoc.15.217

• Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan 10.3762/bjoc.15.217 Abstract Background: Diarylethenes are well-known photochromic compounds, which undergo cyclization and cycloreversion reactions between open- and closed-ring isomers. Recently

• Diarylethenes are well-known photochromic molecules and are widely applied to molecular switches and systems [1][2]. Recently, the photo-switching of fluorescence signals by using diarylethene switches has attracted much attention because of the potential in various optoelectronic applications [3]. For example

Click chemistry towards thermally reversible photochromic 4,5-bisthiazolyl-1,2,3-triazoles

• Chenxia Zhang,
• Kaori Morinaka,
• Mahmut Kose,
• Takashi Ubukata and
• Yasushi Yokoyama

Beilstein J. Org. Chem. 2019, 15, 2161–2169, doi:10.3762/bjoc.15.213

• , Zonguldak Bülent Ecevit University, 67100, Zonguldak, Turkey 10.3762/bjoc.15.213 Abstract Three new diarylethenes were synthesized from 1,2-bis(5-methyl-2-(4-substituted-phenyl)thiazol-4-yl)ethyne and benzyl azide through Ru(I)-catalyzed Huisgen cyclization reactions. The 4,5-bisthiazolyl-1,2,3-triazoles

• electron-withdrawing cyano groups than when they are electron-donating methoxy groups. Keywords: aromatic stabilization energy; diarylethene; ruthenium(I) catalysed Huisgen cyclization; terarylene; thermally reversible photochromism; Introduction Diarylethenes are one of the most widely investigated

• related families of diarylethenes, are largely thermally reversible [10][12] although some are irreversible when the aromatic stabilization energy of the aromatic rings is small [11]. Their syntheses are usually carried out by the sequential construction of the central aromatic ring at the final stage [10

Oxidative and reductive cyclization in stiff dithienylethenes

• Michael Kleinwächter,
• Ellen Teichmann,
• Lutz Grubert,
• Martin Herder and
• Stefan Hecht

Beilstein J. Org. Chem. 2018, 14, 2812–2821, doi:10.3762/bjoc.14.259

• dithienylethenes bearing benzonitrile substituents an additional and rare reductive electrocyclization was observed. The mechanism underlying both observed electrocyclization pathways has been elucidated. Keywords: diarylethenes; electrochromism; molecular switches; (spectro)electrochemistry; Introduction

• Diarylethenes (DAEs) are a rich family of organic photoswitches formally derived from stilbene [1][2]. Upon irradiation they are able to undergo reversible photoisomerization based on 6π-electrocyclization and -cycloreversion, respectively, between two thermally stable states, which make them interesting

The role of alkyl substituents in deazaadenine-based diarylethene photoswitches

• Christopher Sarter,
• Michael Heimes and
• Andres Jäschke

Beilstein J. Org. Chem. 2016, 12, 1103–1110, doi:10.3762/bjoc.12.106

• Christopher Sarter Michael Heimes Andres Jaschke Institut für Pharmazie und Molekulare Biotechnologie, Universität Heidelberg, 69120 Heidelberg, Germany 10.3762/bjoc.12.106 Abstract Diarylethenes are an important class of reversible photoswitches and often claimed to require two alkyl

• substitution pattern, diarylethenes with one alkyl group can exhibit significant photochromism, but they generally show poor stability towards extended UV irradiation, low thermal stability, and decreased fatigue resistance. The results obtained provide an important direction for the design of new efficient

• ][18][19][20][21]. Most reported applications use azobenzenes, while diarylethenes, spiropyrans, fulgides and hemithioindigos are applied less frequently [18][19][20][21][22][23][24][25][26][27][28][29][30]. Diarylethenes are an important class of photoswitches. Originally developed for optical

Direct C–H trifluoromethylation of di- and trisubstituted alkenes by photoredox catalysis

• Ren Tomita,
• Yusuke Yasu,
• Takashi Koike and
• Munetaka Akita

Beilstein J. Org. Chem. 2014, 10, 1099–1106, doi:10.3762/bjoc.10.108

• construction of a Calkenyl–CF3 bond through direct C–H trifluoromethylation of 1,1-disubstituted and trisubstituted aryl alkenes. During the course of our study on the C–H trifluoromethylation of 1,1-diarylethenes 2, we found that a detectable amount of bis(trifluoromethyl)alkenes 4 was formed through double C

Flow microreactor synthesis in organo-fluorine chemistry

• Hideki Amii,
• Aiichiro Nagaki and
• Jun-ichi Yoshida

Beilstein J. Org. Chem. 2013, 9, 2793–2802, doi:10.3762/bjoc.9.314

• gave pentafluorobenzene (PFB) in 92% yield (14.7 kg). Molecular switches based on photochromic diarylethenes are one of the most promising electronic materials [73]. In particular, a number of 1,2-bis(heteroaryl)-substituted perfluorocyclopentenes have been synthesized for use as photosensitive

• stepwise manner via an addition–elimination pathway. However, it is difficult to synthesize unsymmetrical diarylethenes with conventional macro batch systems because of contamination of the symmetrical diarylethenes (two identical nucleophiles are incorporated at the same time). Integrated flow

• microreactor synthesis of photochromic diarylethenes was found to be effective; the generation of heteroaryllithiums and the subsequent nucleophilic addition/elimination with octafluorocyclopentene were successfully achieved (Scheme 12) [75]. As a significant progress, the selective synthesis of unsymmetrical

The effect of the formyl group position upon asymmetric isomeric diarylethenes bearing a naphthalene moiety

• Renjie Wang,
• Shouzhi Pu,
• Gang Liu and
• Shiqiang Cui

Beilstein J. Org. Chem. 2012, 8, 1018–1026, doi:10.3762/bjoc.8.114

• Renjie Wang Shouzhi Pu Gang Liu Shiqiang Cui Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang 330013, PR China 10.3762/bjoc.8.114 Abstract Three new isomeric asymmetric diarylethenes with a naphthyl moiety and a formyl group at the para, meta

• or ortho position of the terminal benzene ring were synthesized. Their photochromism, fluorescent-switch, and electrochemical properties were investigated. Among these diarylethenes, the one with a formyl group at the ortho position of benzene displayed the largest molar absorption coefficients and

• fluorescence quantum yield. The cyclization quantum yields of these compounds increased in the order of para < ortho < meta, whereas their cycloreversion quantum yields decreased in the order of meta > para > ortho. Additionally, all of these diarylethenes functioned as effective fluorescent switches in both

Recent advances towards azobenzene-based light-driven real-time information-transmitting materials

• Jaume García-Amorós and
• Dolores Velasco

Beilstein J. Org. Chem. 2012, 8, 1003–1017, doi:10.3762/bjoc.8.113

• devices. Many different organic photochromic molecules are known in photochemistry, such as azobenzenes, stilbenes, spiropyranes, fulgides, diarylethenes and chromenes among many others (Figure 1) [16]. The photochromic processes that take place when such compounds are illuminated can be divided in three

• to the initial isomer even at elevated temperatures (e.g., fulgides and diarylethenes). ● T-type (thermally reversible type); the photogenerated isomer thermally reverts to the initial form (e.g., azobenzenes, stilbenes or spiropyranes). One of the most used organic chromophores for optical switching

Diarylethene-modified nucleotides for switching optical properties in DNA

• Sebastian Barrois and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2012, 8, 905–914, doi:10.3762/bjoc.8.103

• Sebastian Barrois Hans-Achim Wagenknecht Karlsruhe Institute of Technology (KIT), Institute for Organic Chemistry, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany 10.3762/bjoc.8.103 Abstract Diarylethenes were attached to the 5-position of 2’-deoxyuridine in order to yield three different

• results open the way for the use of diarylethenes as photochromic compounds in DNA-based architectures. Keywords: absorption; cross coupling; molecular switches; oligonucleotide; palladium; photochromism; Introduction The well-defined photoinduced switching of the optical and electronic properties of

• [5][6][7][8], azobenzenes [9], spirobenzopyrans [10] and diarylethenes [11] represent the most promising candidates for introducing photoswitching functionality into biopolymers, and thereby for regulating biological activity [12][13]. Azobenzenes were designed and synthesized as artificial

Molecular switches and cages

• Dirk Trauner

Beilstein J. Org. Chem. 2012, 8, 870–871, doi:10.3762/bjoc.8.97

• features include their absorption spectra, conductivity, geometry and bistability, as well as their polarity, solubility, efficacy, or catalytic activity. Photoswitches are covered extensively, ranging from diarylethenes (Pu, Wagenknecht) to dihydroazulenes/vinylheptafulvenes (Nielsen) and azobenzenes

Anthracene functionalized terpyridines – synthesis and properties

• Falk Wehmeier and
• Jochen Mattay

Beilstein J. Org. Chem. 2010, 6, No. 54, doi:10.3762/bjoc.6.54

• diarylethenes [10][11]. There have also been reports about anthracene functionalized terpyridines in which an anthracene unit was used as a fluorescent sensor [12], spacer [13] or intercalator [14]. Herein we report the synthesis of two twofold anthracene functionalized terpyridines, their iron(II) complexes

A perfluorocyclopentene based diarylethene bearing two terpyridine moieties – synthesis, photochemical properties and influence of transition metal ions

• Falk Wehmeier and
• Jochen Mattay

Beilstein J. Org. Chem. 2010, 6, No. 53, doi:10.3762/bjoc.6.53

• terpyridines linked to dithienylethenes [10][11]. Herein we report the synthesis of terpyridine functionalized diarylethenes based on perfluorocyclopentene, their photochemistry and investigations regarding the influence of transition metals. Results and Discussion Synthetic key steps The basic photochromic

• routes to terpyridine substituted diarylethenes via the above mentioned catalytic cross coupling reactions require suitably functionalized terpyridine precursors, e.g. boronic acid derivatives for Suzuki type cross coupling reactions. 4′-(4-Bromophenyl)-2,2′:6′,2″-terpyridine (7a) and its meta

• inhibition nor any significant slowing of the photoreaction of the ligand was observed. Conclusion We have developed the synthesis of two highly fatigue resistant bis(terpyridinyl) diarylethenes by Suzuki cross coupling methods. The photochemical behavior of the free ligand 10a met our expectations regarding