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  • Self-assembly  (4)
  • photochromes  (3)
  • Koordination  (2)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1421-1428 
    ISSN: 1434-1948
    Keywords: Grid complexes ; Self-assembly ; Co ; Zn ; Coordination chemistry ; Bis(tridentate) ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tretrametallic [2 × 2] grid-type complexes 1-4 are formed by self-assembly of the bis(tridentate) ligands 5 and 6 with ZnII and CoII cations. They have been characterized by spectroscopic studies in solution as well as by crystal structure determination. The substituents in the central pyrimidine ring play an important role in terms of geometry and physical properties of the complexes. They induce an orthogonal orientation of the ligand in the complexes which is critical for the formation of ordered monolayers and extended self-organized arrays of grids. The physical properties of the complexes such as metal-metal interaction and π-π* stacking between the ligands may be modulated by changing these substituents.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1399-1406 
    ISSN: 0947-6539
    Keywords: electrochromes ; fluorescence ; molecular devices ; oligothiophenes ; photochromes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extended dithienylethene compounds 1-3 have been synthesized. They undergo photochromic and electrochemical changes by photoinduced interconversion between open and closed forms of type A and B. In addition, both forms of the N-methylated derivatives 1b and 2b have absorption bands in which excitation results in very large differences in fluorescence between the two forms with very little effect on the opening/closing state, a feature of interest for optical memory data systems. The compounds 2 and 3 contain six and eight conjugated thiophene units in the closed forms, respectively, and thus represent oligothiophenes endowed with a photoactivated switch; they are of special interest in this respect in view of the potential use of switched oligothiophenes in molecular electronic devices.
    Additional Material: 7 Ill.
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  • 3
    ISSN: 0947-6539
    Keywords: diarylethenes ; molecular devices ; nonlinear optics ; photochromes ; redox switches ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic photochromic systems represent a starting point for the elaboration of light-triggered molecular switching devices. The novel bispyridinium and bispyridine compounds 12+ and 6 were synthesized as their uncyclized isomers from 3,5-dibromo-2-methylthiophene in overall yields of 43 and 44%, respectively. The diarylethene photochromes 2 and 10-13, substituted with electron donors and acceptors, were prepared from 5-methylthiophene-2-carboxaldehyde in 21-32% overall yield. All of the compounds were found to exhibit pronounced photochromic properties. Irradiation with UV light resulted in essentially complete photocyclization of the open forms to the intensely coloured closed isomers which could, in turn, be reconverted back to the open state with visible light of γ〉600 nm. The absorption maxima of the described compounds in their closed forms are shifted far towards, and even into, the near-IR region. Whereas no thermochromic properties were observed for the open isomers, the rates of thermal decolouration of the cyclized forms was found to be highly dependent on the nature of the substituents on the thiophene rings. It was demonstrated that reversible photochemical interconversion between the two photochromic states could be used to effectively switch a number of physical properties. Thus, the molecules 12+ and 12 represent two kinds of redox switches, the former in reduction and the latter in oxidation, in which electron conduction is switched on in the closed state and off in the open state. Compound 12 may also be considered to be a photoswitchable analogue of tetrathiafulvalene type substances. On the other hand, compound 2 displays a marked increase in nonlinear optical activity on conversion from the open to the closed form. Such systems are prototypes of photoswitchable molecular wires where electron conduction and push-pull interaction can be reversibly modulated by an external stimulus, namely, irradiation by light.
    Additional Material: 10 Ill.
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  • 4
    ISSN: 0947-6539
    Keywords: diarylethenes ; electrochromes ; molecular devices ; optical memory ; photochromes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bisphenolic dithienylethene molecules 1a and 1b were synthesized in overall yields of 45% from 4-bromoanisole and 44% from 2.6-di-tert-butyl-4-iodophenol, respectively. The corresponding extended quinones 3a and 3b were also prepared. Photochemical studies showed that compounds 1 are photochromic; the open forms 1 could be converted with UV light of 312nm to the closed coloured forms 2 with photostationary states lying at essentially complete conversion (〉 98%). The 1a-2a system was found to exhibit good resistance to photofatigue and thermal stability for both photoisomers. Cyclic voltammetry studies involving the 2/3 couples showed that whereas 2b undergoes irreversible oxidation at + 0.85 V (vs. SCE in THF), the hydroquinone 2a is reversibly oxidized at an E1/2 of + 0.72V (in MeCN, quasi-reversibly in THF at + 0.81 V); this reflects the differences in deprotonation behaviour of the generated QH2/2+ species. The large difference in oxidation potential between 1a and 2a allows the photochemical switching of redox properties. In a complementary fashion, redox switching of the photochromic properties within the 2a-3a pair is possible since 3a is stable to visible light. Owing to this unique behaviour, the triad consisting of 1-3a represents a novel molecular device with mutually regulating photo- and electrochromic behaviour. In addition, the ability to interconvert between the three stable states makes the system well-suited as the basis for an optical memory system with multiple storage and nondestructive readout capacity through a write-lock-read-unlock-erase cycle.
    Additional Material: 11 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 977-982 
    ISSN: 1434-1948
    Keywords: Helicates ; Oligobipyridine ligands ; Self-recognition ; NMR titration ; Self-assembly ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligobipyridine ligands containing one or two imine bridges were found to form double helicates by treatment with copper(I) or silver(I). The properties of the complexes are similar to those of oxapropylene-bridged oligobipyridines. Titration of a mixture of the bis(bipyridine) and the tris(bipyridine) ligands with silver(I) hexafluorophosphate showed that helicates formed with strict self-recognition.
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  • 6
    ISSN: 1434-1948
    Keywords: Self-assembly ; Tetranuclear CuII complex ; [2 × 2] grid-type complex ; Crystal structure ; Magnetic properties ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ditopic ligand 3 has been synthesized. In its deprotonated form, it reacts with copper(II) ions to form a tetranuclear complex 1 of the [2 × 2] CuII4 grid type, the structure of which has been confirmed by X-ray crystallography. Magnetic studies of complex 1 indicate a very weak antiferromagnetic coupling between the phenoxo-bridged CuII ions.
    Additional Material: 3 Ill.
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  • 7
    ISSN: 0044-8249
    Keywords: Cobalt ; Koordination ; N-Liganden ; Selbstorganisation ; Vierkernkomplexe ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 8
    ISSN: 0044-8249
    Keywords: Koordination ; Mehrkernkomplexe ; N-Liganden ; Selbstorganisation ; Silber ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 29 (1990), S. 1304-1319 
    ISSN: 0570-0833
    Keywords: Self-assembly ; Information processing ; Molecular information processing ; Molecular recognition ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The selective binding of a substrate by a molecular receptor to form a supramolecular species involves molecular recognition which rests on the molecular information stored in the interacting species. The functions of supermolecules cover recognition, as well as catalysis and transport. In combination with polymolecular organization, they open ways towards molecular and supramolecular devices for information processing and signal generation. The development of such devices requires the design of molecular components performing a given function (e.g., photoactive, electroactive, ionoactive, thermoactive, or chemoactive) and suitable for assembly into an organized array. Light-conversion devices and charge-separation centers have been realized with photoactive cryptates formed by receptors containing photosensitive groups. Eleclroactive and ionoactive devices are required for carrying information via electronic and ionic signals. Redox-active polyolefinic chains, like the “caroviologens”, represent molecular wires for electron transfer through membranes. Push-pull polyolefins possess marked nonlinear optical properties. Tubular mesophases, formed by organized stacking of suitable macro-cyclic components, as well as “chundle”-type structures, based on bundles of chains grafted onto a macrocyclic support, represent approaches to ion channels. Lipophilic macrocyclic units form Langmuir-Blodgett films that may display molecular recognition at the air-water interface. Supramolecular chemistry has relied on more or less preorganized molecular receptors for effecting molecular recognition, catalysis, and transport processes. A step beyond preorganization consists in the design of systems undergoing self-organization, that is, systems capable of spontaneously generating a well-defined supramolecular architecture by self-assembling from their components under a given set of conditions. Several approaches to self-assembling systems have been pursued: the formation of helical metal complexes, the double-stranded helicates, which result from the spontaneous organization of two linear polybipyridine ligands into a double helix by binding of specific metal ions; the generation of mesophases and liquid crystalline polymers of supramolecular nature from complementary components, amounting to macroscopic expression of molecular recognition; the molecular-recognition-directed formation of ordered solid-state structures. Endowing photo-, electro-, and ionoactive components with recognition elements opens perspectives towards the design of programmed molecular and supramolecular systems capable of self-assembly into organized and functional supramolecular devices. Such systems may be able to perform highly selective operations of recognition, reaction, transfer, and structure generation for signal and information processing at the molecular and supramolecular levels.
    Additional Material: 15 Ill.
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