A new photochromic dispiroanthrabisoxazine

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2179–2180, September, 1990.     

Polarization holographic optical recording based on a new photochromic diarylethene compound

A new unsymmetrical photochromic diarylethene, namely1-[2-methyl-5-(p-N,N-dimethylaminophenyl)-3-thienyl]-2-[2-methyl-5-(3-methoxylphenyl)-3-thienyl] perfluorocyclopentene (1a), was synthesized. The compound showed good photochromism, high sensitivity and remarkable fatigue-resistance both in solution and in poly(methyl methacrylate) (PMMA) matrix with UV/Vis light irradiation. The absorption maximum of its closed-ring isomer was observed at 624 nm in PMMA amorphous film. It is a nice match for the wavelength of the recording laser (633 nm). Using this target compound as recording medium, four types of polarization holographic optical recordings were performed successfully using a He-Ne laser. The results showed that only the orthogonal circular polarization recording could obtain a hologram with high diffraction efficiency and high signal-to noise-ratio. With multiplexing recording technology, three types of polarization multiplexing holographic optical recordings, including angular multiplexing, polarization multiplexing, and angular plus polarization multiplexing holographic recording, were also carried out perfectly based on its photoinduced anisotropic phenomenon accompanying the photochromic reaction by photoirradiation. The results demonstrate that the multiplexing recording technology is an effective method to improve recording capacity when using diarylethene 1 as recording medium.     

Diastereoselectivity in an electrocyclization reaction of cyclopentadienones

Two cyclopentadienones were generated and both underwent conrotatory electrocyclization as expected based on Woodward-Hoffmann rules. This result lends support to the idea that these ring-closing reactions are, in fact, pericyclic processes.     

A photochromic phenoxyquinone based cyanide ion sensor

We have developed a new chemosensor system for cyanide ion that is based on a photochromic material. We observed that addition of cyanide anion to a UV irradiated solution of a phenoxynaphthacenequinone derivative brought about a significant change in the absorption spectra that enabled detection of cyanide ion in a selective and sensitive manner. A carbanion intermediate was shown to be responsible for the long wavelength absorption band (630-940 nm) that is generated by cyanide addition.     

A new photochromic tetra­hydro­indolizine

The title compound, di­methyl 10b′‐(4‐fluoro­styryl)‐8′,9′‐di­methoxy‐4‐nitro‐5′,6′‐di­hydrospiro­[9H‐fluorene‐9,1′(10b′H)‐pyrrolo­[2,1‐a]­iso­quinoline]‐2′,3′‐di­carboxyl­ate, C₃₈H₃₁FN₂O₈, is a new photochromic tetra­hydro­indolizine. One of the C—C bonds at the spiro C atom is very long [1.630 (2) Å], thus explaining the photochromic behaviour.     

A new approach to photorecording based on hindering a phase transition in photochromic chiral liquid crystalline polymers

The phase transition from an 'isotropic smectic phase' to the proper SmA* phase in a new photochromic chiral copolymer can be prevented by illumination with non-polarized white light of low intensity. On the basis of the effect observed, a novel photorecording technique is suggested, so that the shadow image appears as a white scattering texture of the SmA* phase on the background of the transparent, optically isotropic TGB A-like phase. Optical, DSC, and X-ray studies of the polymer are reported, the photorecording set-up is described, and the first written photoimage is presented.     

A fast and stable photochromic switch based on the opening and closing of an oxazine ring

[reaction: see text] We have designed a molecular switch based on the photoinduced opening and thermal closing of an oxazine ring. Ultraviolet excitation of this molecule induces the cleavage of a [C-O] bond to form a p-nitrophenolate chromophore in less than 10 ns with a quantum yield of ca. 0.1. The photogenerated isomer reverts thermally to the original oxazine within 50 ns. Our photochromic switch survives more than 3000 excitation cycles without decomposing, even in air-saturated solutions.     

Inverse photochromic systems based on ketoenamine derivatives

The results of studies into inverse photochromic systems (systems with negative photochromism) based on ketoenamines and ketoenehydrazines of benzo [b]annelated heterocycles and their acylated derivatives carried out at the Institute of Physical and Organic Chemistry at the Rostov State University in the last two decades are summarized.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 506–517, March, 2005.     

A novel photochromic fulgide based on porphyrin for nondestructive information processing

A fulgide connected to porphyrin (FUL-TPP) can transform its open isomer to closed isomer upon the irradiation with UV or visible light. Herein, they can be used to write binary data. Furthermore, the open form can emit luminescence but the closed cannot form while irradiated in another light that will not cause the optical chemical reaction. Therefore, the data can be read out without destruction.     

Recent progresses on diarylethene based photochromic switches

Organic photochromic materials have received considerable attention because of their potential for photonic applications, especially for fast and high density data storage. In 2000, Chemical Reviews published a special issue on photochromic materials including a review about the properties and applications of diarylethene photochromic compounds. Since then much impressive progress has been made in this area. Various new diarylethene derivatives have been prepared and examined. The tutorial review presented herein describes developments in diarylethene-based molecular switches made in the last three years. In addition, the synthetic aspects of diarylethene photochromic compounds, which are important issues and neglected in most previous reviews, have been included.     

A highly selective fluorescent probe for Sn based on a new photochromic diarylethene with a phenol-containing Schiff base unit

A novel diarylethene with a phenol-containing Schiff base unit was successfully synthesized and its multi-responsive photoswitching property was investigated by the stimulation of base/acid and light. The diarylethene showed not only normal photochromism by photoirradiation, but also abnormal photochromism by base and light stimuli. By the stimulation of sodium hydroxide, the absorption maximum of its open-ring isomer showed extraordinarily large redshift of 60 nm, accompanied with a notable color change from colorless to yellow. Subsequent irradiation with 297 nm light further caused a dramatic change in its structure transformation from the deprotonated open-ring isomer to the original closed-ring isomer. Similarly, its deprotonated closed-ring isomer returned to its original open-ring isomer upon irradiation with appropriate visible light. Its deprotonated forms could be restored by the stimulation of hydrochloric acid. Moreover, the diarylethene could be served as a fluorescence probe for recognition of Sn²⁺ with high selectivity.     

Synthesis and properties of a fluorene-capped isotruxene: a new unsymmetrical star-shaped pi-system

An unsymmetrical star-shaped pi-system (1) with an isotruxene core and three fluorene arms has been synthesized, and its photophysical, electrochemical, and thermochemical properties have been investigated and compared with the corresponding symmetrical truxene derivatives 2a-d (Kanibolotsky, A. L.; Berridge, R.; Skabara, P. J.; Perepichka, I. F.; Bradley, D. D. C.; Koeberg, M. J. Am. Chem. Soc. 2004, 126, 13695-13702). Stronger electronic couplings between the arms in 1 vs 2a-d lead to lower optical band gap, larger splitting in oxidation potentials, and superior thermostability. [structure: see text]     

A new selenocyanate-selective electrode based on an Urushi matrix-membrane

Summary A selenocyanate-selective electrode was prepared from tri-n-octylmethylammonium selenocyanate ion-exchanger and a matrix, Urushi. A linear potential-concentration curve was obtained within the concentration range of 10^–1–10^–5 mol/l selenocyanate. When 45–50 wt% of trin-octylmethylammonium selenocyanate ion-exchanger and 55-50 wt% of raw Urushi latex were used, the slope of the linear part of the potential-concentration curve was 60 mV per decade change of the selenocyanate concentration. The static response time was less than 30 s. The electrode exhibited constant potential within the pH range 2–10. The selectivity coefficient for the electrode was measured with the mixed solution method. The electrode was used for the measurement of the formation of selenocyanate from selenious acid, ascorbic acid and potassium cyanide.

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Neue Selenocyanat-selektive Elektrode mit Urushi-Matrixmembran

Zusammenfassung Eine Selenocyanat-selective Elektrode wurde aus einem Tri-n-octylmethylammonium-Selenocyanat-Austauscher und einer Urushi-Matrix hergestellt. Lineare Potential-Konzentrations-Kurven wurden im Konzentrationsbereich 10^–1 bis 10^–5 mol/l Selenocyanat erhalten. Bei Einsatz von 45–50% Tri-n-octylmethylammonium-Selenocyanat und 55-50% rohem Urushi-Latex betrug die Neigung des linearen Teils der Potential-Konzentrationskurve 60 mV pro Zehnerpotenz Selenocyanatkonzentration. Die statische Ansprechzeit war weniger als 30 s. Die Elektrode wies im pH-Bereich von 2–10 ein konstantes Potential auf. Der Selektivitätskoeffizent wurde nach der Methode der Lösungsgemische gemessen. Die Elektrode wurde angewendet zur Messung der Bildung von Selenocyanat aus seleniger Säure, Ascorbinsäure und Kaliumcyanid.

     

New photochromic xerogels composites based on nitrosyl complexes

New photoswitchable hybrid materials based on mononitrosyl complexes with excellent optical properties have been obtained by sol–gel process. Inclusion in silica matrix prepared from tetramethoxysilane precursor leads to new materials in which the ruthenium complex [RuCl(NO)py₄](PF₆)₂·1/2H₂O (py = pyridine) is stabilized as crystalline nanoparticles with diameters between 2 and 15 nm. Photochromic properties are maintained and have been evidenced by infrared spectroscopy under irradiation (λ = 473 nm) at low temperature (T = 100 K). The reversible transfer from the ground state (GS) to the metastable state (MS1) is about 40% in the composite, which is close to the value observed on the most studied sodium nitroprusside (50% on pure material).     

Structure of a new photochromic indoline spiropyran

Conclusions An x-ray diffraction structural study was carried out for the photochromic spirpyran 1,3,3-trimethyl-5-nitrospiro(indoline-2,2-[2H-1]-benzopyran). The C_spiro-O bond in the spiropyran is longer than the normal value but shorter than in the isomeric spiropyran with the nitro group in the benzopyran fragment, which is characterized by a higher quantum yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 191–194, January, 1985.     

Multistate/multifunctional switches based on photochromic Schiff base

The salicylidene Schiff base derivative, namely, N-salicylidene-(S)-alpha-naphthylethylamine (SNEA) has been synthesized to study the characterization of multistate/multifunctional switches. Upon the stimulations of optical inputs (UV light and visible light) and chemical inputs (pH and Zn(2+)), SNEA undergoes reversible photochromism, deprotonation and complexation reactions. In this case, four chemical species are involved. These interconversions of SNEA between four states have been systematically investigated by the absorption and the emission spectra. Spectroscopic studies indicate that the photochromic switch, pH switch and fluorescent switch can be realized using the single molecular entity of SNEA.     

Photonics of nanostructured systems based on photochromic spiro compounds

A review of the results of studies on photoinduced aggregation of photochromic spiro compounds of the class of spiropyrans and spirooxazines is presented. The possibility to form aggregates of photoinduced species of various types, in particular, H and J aggregates, in liquid and solid polymer solutions as well as in photochromic polymers, amorphous films, and mono-and polymolecular layers is shown. The main fields of applications of nanostructured photochromic systems are considered.     

A new metallostar complex based on an aluminum(iii) 8-hydroxyquinoline core as a potential bimodal contrast agent

A ditopic DTPA monoamide derivative containing an 8-hydroxyquinoline moiety was synthesized and the corresponding gadolinium(iii) complex ([Gd(H5)(H(2)O)](-)) was prepared. After adding aluminum(iii), the 8-hydroxyquinoline part self-assembled into a heteropolymetallic triscomplex [(Gd5)(3)Al(H(2)O)(3)](3-). The magnetic and optical properties of this metallostar compound were investigated in order to classify it as a potential in vitro bimodal contrast agent. The proton nuclear magnetic relaxation dispersion measurements indicated that the relaxivity r(1) of [Gd(H5)(H(2)O)](-) and [(Gd5)(3)Al(H(2)O)(3)](3-) at 20 MHz and 310 K equaled 6.17 s(-1) mM(-1) and 10.9 s(-1) mM(-1) per Gd(iii) ion respectively. This corresponds to a relaxivity value of 32.7 s(-1) mM(-1) for the supramolecular complex containing three Gd(iii) ions. The high relaxivity value is prominently caused by an increase of the rotational tumbling time τ(R) by a factor of 2.7 and 5.5 respectively, in comparison with the commercially used MRI contrast agent Gd(iii)-DTPA (Magnevist?). Furthermore, upon UV irradiation, [(Gd5)(3)Al(H(2)O)(3)](3-) exposes green broad-band emission with a maximum at 543 nm. Regarding the high relaxivity and the photophysical properties of the [(Gd5)(3)Al(H(2)O)(3)](3-) metallostar compound, it can be considered as a lead compound for in vitro bimodal applications.     

Photoswitching of an alcohol-sensitive photochromic diarylethene

The closed-ring isomer of diarylethene 1a, 1-(2-methyl-5-(4-N,N-diethylaminophenyl)thien-3-yl)-2-(2-methyl-5-phenylthien-3-yl)perfluorocyclopentene was found to cause the substitution reaction with primary alcohols at room temperature. The open-ring isomer 1a was stable in the alcohols. The product obtained in methanol was isolated by HPLC, and the structure was identified by ¹H NMR, mass spectrometry, and X-ray crystallographic analysis. It was revealed that two fluorine atoms were replaced with methoxy groups. The substitution reaction was also caused with ethylene glycol to form the five-membered ring. Both the products also showed photochromism, and had absorption maxima and photocycloreversion quantum yields different from those of 1a.