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  • General Chemistry  (172)
  • Chirality  (5)
  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1585-1595 
    ISSN: 0947-6539
    Schlagwort(e): concave hydrocarbons ; cyclophanes ; host/guest chemistry ; ion-selective electrodes ; prismands ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Concave hydrocarbons, such as 1 (C36H36), 4 (C60H60), 5 (C54H48), and 6 (C60H52), represent three-dimensionally clamped analogues of π-prismands. They encapsulate small metal ions and accomplish metal-ion extraction from aqueous solution. Their remarkable selectivity allows applications such as incorporation in ion-selective electrodes. The synthetic route is based on well-established cyclophane methodology and, thus, offers a general approach to a whole family of concave hydrocarbons.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1491-1509 
    ISSN: 1434-193X
    Schlagwort(e): Chirality ; Circular dichroism ; Cyclophanes ; Theoretical calculations ; Strained molecules ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The chiroptical properties of planar-chiral and helical molecules without stereogenic centres and with well-defined structure, strain, electronic properties and chirality are investigated by experimental and theoretical circular dichroism spectroscopy. We report on the synthetic and theoretical achievements made during the past 10 years in the field of rigid [2.2]metacyclophane propellers, as well as in the area of [n]para- and [n]metacyclophanes containing aliphatic parts like adamantane or unsaturated bridges. Results for carbo and hetero helicenes and helicene-related molecules like twisted phenanthrenes are presented. It is demonstrated how reliable theoretical calculations using configuration interaction and time-dependent methods in combination with density functional theory today are and how useful the interplay between theory and experiment stimulates the development of chiral molecules optimized for this purpose. Even for large molecules it is routinely possible to assign Cotton effects to electronic transitions, to evaluate chromophore contributions, to determine absolute configurations and conformational equilibria, and to discover intramolecular charge transfer effects.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1434-193X
    Schlagwort(e): Supramolecular chemistry ; Rotaxanes ; Mechanical bond ; Molecular recognition ; Chirality ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this paper we report on amide rotaxanes with tetrabenzoylglucose stoppers. When acetyl groups are used instead of benzoyl groups, merely a pseudo-rotaxane 5 is obtained. The circular dichroism measurements of the rotaxanes 6a and 6b differ significantly from that one of the free axle 7. Similarly, the Cotton effects of the mixtures of achiral wheels 2a and 2b and chiral axle indicate intermolecular host-guest interactions, likewise. After an addition of a solution of NaOMe the wheel is slipping off immediately and quantitatively by hydrolysis, as the benzoylglucose stoppers decrease in size by hydrolysis.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1471-1477 
    ISSN: 1434-193X
    Schlagwort(e): Cyclophanes ; Dilution principle ; Heterocycles ; Medium membered rings ; Ring strain ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The N-protected 1,10-diaza[2.2]metacyclo- and 1,10-diaza-[2]metacyclo[2](2,6)-pyridinophanes 4 and 5 have been synthesized for the first time using high dilution conditions. The free secondary diamine 7 was obtained from 4 by alkaline hydrolysis. - Quantum chemical calculations support the hypothesis that 7 is one of the most strained anti-hetera[2.2]metacyclophanes known. This is also evident from the 1H-NMR spectrum of 7, which shows one of the strongest high field shifts for the intraannular protons in comparison to other anti-[2.2]metacyclophanes.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 155-161 
    ISSN: 1434-193X
    Schlagwort(e): Mechanical bonding ; Interlocked molecules ; Template synthesis ; Calixarenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of the amide-based rotaxane 7a bearing calix[4]arene blocking groups is described for the first time. While rotaxane formation fails if a calix[4]arene is functionalized at the upper rim with only an amino or methylamino group lacking any spacer, the prolonged amine 5a works successfully as stopper unit preventing dethreading of the dimeric wheel 1a by its size. Rotaxane formation of 8b was observed only by MALDI-TOF mass spectrometry of the reaction mixture of the amine 5b, the axle 6 and 1a. With the larger trimeric wheel 1b no stable rotaxane could be obtained. It either does not act as a concave template or its opening is too wide, even for the bulky calixarene stoppers.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 499-505 
    ISSN: 1434-193X
    Schlagwort(e): Catenanes ; Molecular recognition ; Template effect ; Mechanical bond ; Key-lock interaction ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---[3]Catenanes of the amide type were synthesized preparatively for the first time. Large macrocycles bearing two guest-binding sites were used to synthesize these amide-linked [3]catenanes in yields of 4%, either by formation of rigid macrocyclic boxes, or with macrocycles consisting of flexible long-chained aliphatic diamines. Furthermore, the systematic introduction of 1,ω-alkane diamines as building blocks for catenanes is described. The synthesis of a series of [2]catenanes by varying the ring size of one of the two macrocycles was also achieved in yields of 10%.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 1233-1238 
    ISSN: 1434-193X
    Schlagwort(e): Electrophilic additions ; Bromine addition to double bonds ; Hydrogenation of double bonds ; Rotaxanes ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: -Here we report on the possibility of using rotaxane wheels as noncovalent protecting groups which significantly decrease the activity of functional groups in the central part of the axle. The amide-linked rotaxanes 5aand 5b, each containing a C=C double bond in their axle, have been synthesised. The catalytic hydrogenation of these two rotaxanes proceeds slower than those of the corresponding free axle compounds 6a and 6b, indicating steric hindrance of the C=C double bond by the wheel of the rotaxane in each case. Nontheless, the rotaxane 9with an aliphatic (succinic acid) middle region in its axle can be prepared in this manner. Dehydrobromination of the axle in the rotaxane 15yields the rotaxane 16 with a C≡C triple bond located in the centre of the axle.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 640-643 
    ISSN: 0947-6539
    Schlagwort(e): lactam ; macrocycles ; rotaxanes ; self-assembly ; template syntheses ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two new rotaxane types, the [2]rotaxanes 12a,b and the [3]rotaxane 13, have been synthesised by treating the “axle” 7 with the stopper component 9 in the presence of the “wheel” 8. A nonionic template intermediate of type 10 is proposed. The [3]rotaxane 13 was only obtained when the chain of the “axle” had a certain length: with n = 1 only [2]rotaxane 12 a was isolated, whereas with n = 2 the [3]rotaxane 13 was formed besides the [2]rotaxane 12 b. This suggests that more extended rotaxanes and polyrotaxanes can be synthesised by the template strategy.
    Materialart: Digitale Medien
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  • 9
    ISSN: 0947-6539
    Schlagwort(e): macrocycles ; rotaxanes ; sulfon-amides ; supramolecular chemistry ; template synthesis ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The preparative syntheses of new nano-sized rotaxane assemblies are described, namely, of the first tris[2]rotaxane, 15, the first bis[2]rotaxane connected at the axles, 4, and the first [3]rotaxane with two different axles, 12 (unsymmetrical “bis[2]rotaxane”). These syntheses were made possible by the directed incorporation of a sulfonamide group into the amide-linked rotaxane building blocks. The sulfonamide moiety can be used as a functional group in alkylation reactions, allowing the further attachment of building blocks in good yields. The successful synthesis of these new rotaxane architectures demonstrates the synthetic potential of this sulfonamide strategy in the preparation of multirotaxane and dendritic rotaxane structures.
    Materialart: Digitale Medien
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  • 10
    ISSN: 0947-6539
    Schlagwort(e): bipyridine ligands ; dendrimers ; dioxygen quenching ; luminescence ; ruthenium ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Several synthetic strategies have been explored to prepare dendrimers having the [Ru(bpy)3]2+ complex as their core (bpy = 2,2′-bipyridine). Dendritic ligands have been synthesized by attaching branches in the 4,4′-positions of bpy. The largest dendritic bipyridine ligand contains 54 peripherical methylester units. Four RuII dendritic complexes have been prepared. Their absorption and emission spectra are very similar to those of the unsubstituted parent RuII-bipyridine complexes. The large dendritic complexes, however, exhibit a more intense emission and a longer excited-state lifetime than [Ru(bpy)3]2+ in aerated solutions. This is due to the shielding effect of the dendrimer branches on the Ru-bipyridine core, which limits the quenching effect of molecular oxygen. For the largest dendritic complex, which contains 54 peripherical methylester units, the excited-state lifetime in aerated acetonitrile solution is longer than 1 μs, and the rate constant for dioxygen quenching is twelve times smaller than for [Ru(bpy)3]2+.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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