Photochromic heterocyclic fulgides. Part 4. The thermal and photochemical reactions of (E)-isopropylidene-[α-(2- and -(3-thienyl)ethylidene]succinic anhydrides and related compounds

Glaze, Alan P.; Harris, Stuart A.; Heller, Harry G.; Johncock, W.; Oliver, S. N.; Strydom, Peter J.; Whittall, John

doi:10.1039/p19850000957

Cited by 59 publications

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“…The isopropyl derivative 5b improves the colouring efftciency compared to the ordinary thiophenefulgide Sa ( = 2-[ l-( 2,5dimethyl-3-thienyl)ethylidene]-3-isopropylidene succinic anhydride) [ 6,8]. The quantum yield for colouring is fairly promoted by the extreme sterical hindrance caused by the isopropyl substituent.…”

Section: Discussionmentioning

confidence: 97%

Section: Intmductionmentioning

confidence: 99%

“…In most cases, ring closure and ring opening reactions follow the Woodward-Hoffmann rules [ l-9,13 1. Heller and his group [3][4][5][6] found that alkyl-substituted heterocyclic fulgides show high reversibility ("fatigue resistance") along with thermal stability.As far as any practical application of photochromic materials is concerned, high efficiencies of the photochromic processes are desirable. Some years ago, predictions (based on semiempirical PPP-calculations) were made how to optimize the quantum yield for the colouring process [ 191.…”

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confidence: 99%

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Photochromic thiophenefulgides. Photokinetics of two isopropyl derivatives

et al. 1991

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For two photochromic isopropyl-thiophenefulgides a complete photokinetic analysis is given. For one compound (Sb), the partial quantum yield for the coloming process (&c= 54%) is the highest value found for thiophenefulgides. EZ-isomerisations do not play an important role. The colouringquantum yield is temperature independent down to 20 K, whereas bleaching requires little thermal activation. In case of an adamantylidene substituted isopropyl-thiophenefulgide (Sc), the bleaching efficiency (@cs= 3 1%) is very high. Upon heating of the cyclic products, thermal bleaching occurs with an activation energy of 1 eV. IntmductionArylfulgides are capable of two different types of reversible photoreactions: EZ-isomerisations and ring closure reactions [ l-3,8,9,1 1,15-17 1. Whereas the former ones are accompanied by only a slight colour change, the colour is altered dramatically during the latter ones. Therefore, the reversible cyclisation reactions are referred to as photochromism of fulgides. In most cases, ring closure and ring opening reactions follow the Woodward-Hoffmann rules [ l-9,13 1. Heller and his group [3][4][5][6] found that alkyl-substituted heterocyclic fulgides show high reversibility ("fatigue resistance") along with thermal stability.As far as any practical application of photochromic materials is concerned, high efficiencies of the photochromic processes are desirable. Some years ago, predictions (based on semiempirical PPP-calculations) were made how to optimize the quantum yield for the colouring process [ 191. According to these results, bulky substituents R' (increasing sterical hindrance and constraints of the exocyclic double bond) should increase the colouring quantum yield and lower the efficiencies for EZ-isomerisations and radiationless deactivations. On the other hand, it has been shown [ 3,9] that bleaching efficiency of some furanfulgides is enhanced by introduction of the adamantylidene group R". (see scheme 1).Applying these concepts, isopropyl-and adamantylidene substituted thiophenefulgides were synthesized. We report here a complete photokinetic analysis of the different isomerisations of these compounds. Furthermore, we studied the temperature dependence of the photochromic behaviour including thermal bleaching.

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Section: Discussionmentioning

confidence: 97%

Section: Intmductionmentioning

confidence: 99%

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Photochromic thiophenefulgides. Photokinetics of two isopropyl derivatives

et al. 1991

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“…The fulgides (Z)-1a [18] (Scheme 2) and (E)-1b [19] (Scheme 3) were synthesized by Stobbe condensation [20] of diethyl or dimethyl isopropylidenesuccinate with (2,5-dimethyl-3-thienyl) methyl ketone and (2,5-dimethyl-3-thienyl) isopropyl ketone, respectively, followed by hydrolysis and subsequent cyclization of the resulting diacids with acetic anhydride or dicyclohexylcarbodiimide. Separation of the major isomers was achieved by chromatography or crystallization.…”

Section: Synthesismentioning

confidence: 99%

“…[9] Heller et al [11,12] described the synthesis of furyl-and arylfulgimides by treatment of succinic hemi-esters with Grignard salts of primary amines and subsequent cyclization to the imide with acetyl chloride in 35% yield. Recently, Rentzepis [17] reported the synthesis of N-alkyl-and N-aryl-2-indolylfulgimides by ZnCl 2 or ZnBr 2 in the presence of HMDS (1,1,1,3,3,3-hexamethyldisilazane) in benzene at high temperature in 80Ϫ90% yield.…”

Section: Introductionmentioning

confidence: 99%

Syntheses and UV/Vis Properties of Amino‐Functionalized Fulgimides

Otto

Rück‐Braun

2003

Eur J Org Chem

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Functionalized fulgimides are regarded as a promising class of photochromic compounds for modulating the structure and function of biomolecules. A new synthetic route to fulgimides bearing amino‐functionalized substituents at the imide nitrogen atom has been developed. The synthesis of the fulgimides has been achieved by base‐catalyzed cyclization of phenacyl esters of the succinamic acids derived from fulgides and N‐Boc‐protected alkyl‐ and aryl‐substituted diamines with triethylamine or tert‐butyllithium. The UV/Vis spectroscopic data and the photochromic properties of these new compounds have been studied. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Information Storage Materials, Optical

Kämpf¹,

Mergel²

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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In addition to the established magnetic mass storage media (floppy disk, hard disk, tape) optical mass storage media (CD‐ROM (compact disk‐read only memory), WORM (write once, read many times), EOD (erasable optical disk)) are increasingly used. Generally, magnetic and optical media do not compete, but complement each other due to their specific advantages. Progress in optical data storage technology is closely connected with the development of suitable materials. This article illustrates in detail the current state of the art and the ongoing development of materials for optical data storage. For the information layer of WORM disks, dyes with high ir absorption, low heat conductivity, and good solubility are required. Besides polymethine dyes, biaxially substituted silicon–naphthalocyanines are used; also combinations of metal complexes are employed. The magneto‐optical materials for EOD‐disks in MOR (magneto‐optical recording) technique are primarily ferrimagnetic ternary amorphous alloys of rare‐earth (RE) and transition‐metals (TM) (GdTbFe, TbFeCo, DyFeCo). Ferrites with spinel‐ or garnet‐structure, eg, rare‐earth iron‐garnets (RIG), are commercially unimportant mainly due to their high deposition temperature. Co/Pt‐multilayers (MLs) exhibit interesting properties, but are still waiting for commercial introduction. Research concentrates on exchange‐coupled RE‐TM layers, which permit a direct overwrite procedure. Phase‐change materials for EOD‐disks in PCR (phase‐change recording) technique are primarily ternary alloys (eg, GeSbTe, InSbTe). Research focuses on materials with fast crystallization in parallel with high stability even at numerous write/read/erase cycles. As substrate materials for CD‐ROM disks, end group‐modified bisphenol A–polycarbonate (BPA‐PC) is employed exclusively. For WORM and EOD disks mainly BPA‐PC and sometimes glass is applied.

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Photochromic heterocyclic fulgides. Part 4. The thermal and photochemical reactions of (E)-isopropylidene-[α-(2- and -(3-thienyl)ethylidene]succinic anhydrides and related compounds

Abstract: Photochromic Heterocyclic Fulgides. Part 4.' The Thermal and Photochemical Reactions of ( E )lsopropyl idene-[a-(2and -(3-t h ienyl)ethyl idene]succinic Anhydrides and Related Compounds

Cited by 59 publications

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Photochromic thiophenefulgides. Photokinetics of two isopropyl derivatives

Photochromic thiophenefulgides. Photokinetics of two isopropyl derivatives

Syntheses and UV/Vis Properties of Amino‐Functionalized Fulgimides

Information Storage Materials, Optical

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