154566-69-5Relevant articles and documents
Reversible photochromism of novel silver(I) coordination complexes with 1,2-bis(2′-methyl-5′-(2″-pyridyl)-3′-thienyl)perfluorocyclopentene in crystalline phase
Munakata, Megumu,Han, Jing,Nabei, Atsuhiro,Kuroda-Sowa, Takayoshi,Maekawa, Masahiko,Suenaga, Yusaku,Gunjima, Nozomu
, p. 4281 - 4288 (2006)
Three novel silver(I) complexes with 1,2-bis(2-methyl-5′-(2″-pyridyl)-3′-thienyl)perfluorocyclopentene (BM-2-PTP) were synthesized by the reaction of Ag(CF3SO3) or Ag(CF3COO) with BM-2-PTP in benzene at different temperatures. The structures of these metal complexes were revealed by X-ray crystallographic analyses and the correlation between crystal structures and photochromic performance was discussed. In complexes 1 and 2, silver(I) is three-coordinated to two nitrogens from distinct ligand molecules as well as one oxygen from anions to form a 1-D polymeric structure. On the other hand, complex 3 contains two crystallographic independent Ag(I) with different coordination environments, and the adjacent BM-2-PTP molecules are connected by Ag-CF3CO2-Ag chains to afford a 1-D double chain structure. The difference in structures of three complexes shows the interesting anionic effect on coordination and the subtleness of crystal engineering. It is noted that complex 3 underwent reversible photochromic reaction in crystalline state despite the unfavorable framework to the rotation of thiophene groups.
Guest-Induced Structural Transformations in a Porous Halogen-Bonded Framework
Nikolayenko, Varvara I.,Castell, Dominic C.,van Heerden, Dewald P.,Barbour, Leonard J.
, p. 12086 - 12091 (2018)
Structural evidence obtained from in situ X-ray diffraction shows that halogen bonding is responsible for the formation of a dynamic porous molecular solid. This material is surprisingly robust and undergoes reversible switching of its pore volume by activation or by exposure to a series of gases of different sizes and shapes. Volumetric gas sorption and pressure-gradient differential scanning calorimetry (P-DSC) data provide further mechanistic insight into the breathing behavior.
Packing Structure Effects on the Slow Magnetic Relaxation Pathways of Dysprosium (III) Complexes
Kamila, Mritunjoy,Cosquer, Goulven,Breedlove, Brian K.,Yamashita, Masahiro
, p. 595 - 603 (2017)
Three complexes, [Dy{5-(5-methylthiophen-2-yl)-2,2- bipyridine}(hfac)3] (6), [Dy{5-(4-bromo-5-methylthiophen-2- yl)-2,2-bipyridine}(hfac)3] (7) and [Dy{5-(4-ethynyl-5-methylthio- phen-2-yl)-2,2-bipyridine}(hfac)3] (8) (hfac = hexafluoroacetylacetate), were synthesized to investigate the effects of substituents on the ligand far from the metal ion on the magnetic properties of the dysprosium ion. 7 crystallized in two polymorphs (P21/n for 7a and P21/a for 7b), whereas 6 and 8 crystallized in one polymorph (P21/n and P21/a, respectively). All of the complexes have columnar structures, and in 6 and 7a, there are stacking interactions between neighboring aromatic rings in contrast to compounds 7b and 8, which do not show such interactions. Every complex underwent slow magnetic relaxation with a single relaxation time, except for complex 7a, for which there were two relaxation times. In order to clarify the role of distal substitution and crystal packing, the magnetic properties were studied in solution, where all of the complexes show single relaxation times.
Photoactivation of the cytotoxic properties of platinum(II) complexes through ligand photoswitching
Presa, Andreu,Vázquez, Guillem,Barrios, Leoní A.,Roubeau, Olivier,Korrodi-Gregório, Luís,Pérez-Tomás, Ricardo,Gamez, Patrick
, p. 4009 - 4022 (2018)
The development of photoactivatable metal complexes with potential anticancer properties is a topical area of current investigation. Photoactivated chemotherapy using coordination compounds is typically based on photochemical processes occurring at the metal center. In the present study, an innovative approach is applied that takes advantage of the remarkable photochemical properties of diarylethenes. Following a proof-of-concept study with two complexes, namely, C1 and C2, a series of additional platinum(II) complexes from dithienylcyclopentene-based ligands was designed and prepared. Like C1 and C2, these new coordination compounds exhibit two thermally stable, interconvertible photoisomers that display distinct properties. The photochemical behavior of ligands L3-L7 has been analyzed by 1H NMR and UV-vis spectroscopies. Subsequently, the corresponding platinum(II) complexes C3-C7 were synthesized and fully characterized, including by single-crystal X-ray diffraction for some of them. Next, the interaction of each photoisomer (i.e., containing the open or closed ligand) of the metal complexes with DNA was examined thoroughly using various techniques, revealing their distinct DNA-binding modes and affinities, as observed for the earlier compounds C1 and C2. The antiproliferative activity of the two forms of the complexes was then assessed with five cancer cell lines and compared with that of C1 and C2, which supported the use of such diarylethene-based systems for the generation of a new class of potential photochemotherapeutic metallodrugs.
Switchable Mesomeric Betaines Derived from Pyridinium-Phenolates and Bis(thienyl)ethane
Adams, J?rg,Dahle, Sebastian,Hübner, Eike G.,Lederle, Felix,Maus-Friedrichs, Wolfgang,Nagorny, Sven,Schmidt, Andreas,Udachin, Viktor,Weingartz, Thea
, p. 3178 - 3189 (2021/07/02)
Syntheses of push–pull substituted non-symmetric bis(thienyl)ethenes (BTEs) possessing a central perfluorocyclopentene core are described. The substituent effects of anisole, phenole, and phenolate as well as pyridine, pyridinium, and N-methylpyridinium substituents, joined through their 3- or 4-positions to the central BTE core, respectively, cover the range from very strongly electron-donating [σ(4-phenolate)=?1.00] to extremely strongly electron-withdrawing [σ(pyridinium-4-yl)=+2.57] in the title mesomeric betaines. The different isomers possessing 4-yl/4-yl, 4-yl/3-yl and 3-yl/3-yl substituents represent different combinations of conjugated and cross-conjugated partial structures and cause different spectroscopic properties. In addition, through-space conjugation between the 2- and 2′-position of the thiophenes can be observed which circumvents the charge-separation of through-bond cross-conjugation. The BTE possessing the push–pull chromophore consisting of 3-anisole and 4-pyridinium substituents (24) displays the best extinction coefficients within the series of compounds described here (?=33.8/15.7 L/mol ? cm), while the mesomeric betaine possessing an N-methylpyridinium-4-yl and a 4-phenolate substituent (29) displays considerable bathochromic shifts to λmax=724 nm in its closed form.
Development of Red-Shifted and Fluorogenic Nucleoside and Oligonucleotide Diarylethene Photoswitches
Kolmar, Theresa,Becker, Antonia,Pfretzschner, Ronja A.,Lelke, Alina,J?schke, Andres
supporting information, p. 17386 - 17394 (2021/10/20)
The reversible modulation of fluorescence signals by light is of high interest for applications in super-resolution microscopy, especially on the DNA level. In this article we describe the systematic variation of the core structure in nucleoside-based diarylethenes (DAEs), in order to generate intrinsically fluorescent photochromes. The introduction of aromatic bridging units resulted in a bathochromic shift of the visible absorption maximum of the closed-ring form, but caused reduced thermal stability and switching efficiency. The replacement of the thiophene aryl unit by thiazol improved the thermal stability, whereas the introduction of a benzothiophene unit led to inherent and modulatable turn-off fluorescence. This feature was further optimized by introducing a fluorescent indole nucleobase into the DAE core, resulting in an effective photoswitch with a fluorescence quantum yield of 0.0166 and a fluorescence turn-off factor of 3.2. The site-specific incorporation into an oligonucleotide resulted in fluorescence-switchable DNA with high cyclization quantum yields and switching efficiency, which may facilitate future applications.
Development of High-Performance Pyrimidine Nucleoside and Oligonucleotide Diarylethene Photoswitches
Kolmar, Theresa,Büllmann, Simon M.,Sarter, Christopher,H?fer, Katharina,J?schke, Andres
supporting information, p. 8164 - 8173 (2021/03/08)
Nucleosidic and oligonucleotidic diarylethenes (DAEs) are an emerging class of photochromes with high application potential. However, their further development is hampered by the poor understanding of how the chemical structure modulates the photochromic properties. Here we synthesized 26 systematically varied deoxyuridine- and deoxycytidine-derived DAEs and analyzed reaction quantum yields, composition of the photostationary states, thermal and photochemical stability, and reversibility. This analysis identified two high-performance photoswitches with near-quantitative, fully reversible back-and-forth switching and no detectable thermal or photochemical deterioration. When incorporated into an oligonucleotide with the sequence of a promotor, the nucleotides maintained their photochromism and allowed the modulation of the transcription activity of T7 RNA polymerase with an up to 2.4-fold turn-off factor, demonstrating the potential for optochemical control of biological processes.
Norbornadiene-bridged diarylethenes and their conversion into turn-off fluorescent photoswitches
Büllmann, Simon M.,J?schke, Andres
supporting information, p. 7124 - 7127 (2020/07/14)
We describe the synthesis and characterization of novel diarylethene photoswitches that contain a norbornadiene bridge and operate as p-type positive photochromes. One of the double bonds of norbornadiene is furthermore utilized to attach a fluoresceine tetrazine by an iEDDA cascade reaction, thereby forming a turn-off mode fluorescent photoswitch. This journal is
Photochromic dithienylethenes characterized by: In situ irradiation NMR-spectroscopy and electrochemically induced responsiveness on gold substrates
Von Irmer, Jonas,Frie?, Florian,Herold, Dominik,Kind, Jonas,Thiele, Christina M.,Gallei, Markus
supporting information, p. 14088 - 14097 (2019/12/02)
Photochromic compounds comprising small molecules and polymers have been shown to be of great interest in the field of stimuli-responsive materials for applications as sensors and (nano-) devices. In this regard dithienylethenes (DTEs) have been proven to be especially valuable because of their tolerance to chemicals and their good stability making them tunable and reversibly switchable between an open and a closed structure featuring different optical properties. By utilizing a potent in situ irradiation NMR spectroscopy approach, it is possible to determine the photochromic switching capability of two DTE derivatives in solution leading to crucial information about the structures, the equilibria of the chemical ring-opening and closing of the DTEs as well as the longtime stability of these molecular switches. In particular the perfluorinated thioether bearing compound shows remarkable stability with little fatigue related to the irreversibly cyclized byproduct known for DTEs. The thioether-bearing DTEs can be deprotected and used for immobilization on gold substrates which are characterized by water contact angle measurements prior to and after DTE functionalization. Finally, the electrochemically induced switching capability of the perhydro DTE is investigated by cyclic voltammetry proving its fast, quantitative and reversible cyclization. We envisage these materials for applications as sensors and optical switching devices.
Symmetric 9,10-bisthienylanthracene compound, and preparation method and application thereof
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Paragraph 0076; 0078, (2019/10/01)
The invention especially relates to a symmetric 9,10-bisthienylanthracene compound, belonging to the technical field of aggregation-induced luminescent materials. According to the invention, a styrylgroup in a traditional anthracene compound is substituted by a thiofuran biphenyl group so as to obtain the symmetric 9,10-bisthienylanthracene compound with a simple molecular structure and obvious AIE properties. The molecular end of the compound is easily modified by changing different groups so as to regulate the luminescent properties of the compound. The symmetric 9,10-bisthienylanthracene compound of the invention can be obtained by a simple Suzuki coupling reaction; raw materials used in the invention are low in cost, and the compound is simple to synthesize and favorable for industrial production and has great application prospects. The compounds BMPTA, BPTA and BCPTA can be used as fluorescent markers for HeLa cells and have potential application value in the field of cell dyes;and the compounds BMPTA and BPTA have obvious mechanical discoloration characteristics, and can be used for preparing mechanical force-regulated illuminating elements and the like.
