Structure and kinetics of novel cyclophane inclusion compounds

Apel, Sylke; Czugler, Mátyás; Griffith, Vivienne J.; Nassimbeni, Luigi R.; Weber, Edwin

doi:10.1039/a702583a

Cited by 5 publications

(3 citation statements)

References 11 publications

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“…Diphenylmethane (DPM) and some of its derivatives are frequently used in the construction of macrocycles,8 catenanes,9 rotaxanes9a, 10 and other host molecules 11. This subunit provides an electron‐rich zone able to facilitate the complexation of the guest, especially in neutral hosts;8d–8j, 8m, 11e the face‐to‐face arrangement being the optimal conformation for the formation of host–guest complexes in most cases. However, the DPC subunit is far from being rigid, even when placed in the structure of macrocycles.…”

Section: Resultsmentioning

confidence: 99%

Influence of Highly Preorganised 7,7-Diphenylnorbornane in the Free Energy of Edge-to-Face Aromatic Interactions

2001

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The influence of preorganised 7,7-diphenylnorbornane in the stability (Ka) of host-guest complexes as well as in the determination of the energy of edge-to-face aromatic interactions has been investigated. The guest molecules studied bind more strongly with hosts that contain the cofacial 7.7-diphenylnorbornane subunit than with similar hosts that have a 1,1-diphenylcyclohexane subunit. On the other hand, the value of the edge-to-face aromatic interactions calculated for our complexes (-0.2 +/- 0.6 kJmol(-1)) is significantly lower (by a factor of seven) than the one previously reported in the literature. This result highlights the importance of entropic factors in the determination of weak noncovalent interactions.

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Section: Resultsmentioning

confidence: 99%

Influence of Highly Preorganised 7,7-Diphenylnorbornane in the Free Energy of Edge-to-Face Aromatic Interactions

2001

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“…19 Solutions of 1 (2.6 g, 7.5 mmol) in dry acetone (250 ml) and of 2,5-dimethoxy-1,3-bis(bromomethyl)benzene (2.4 g, 7.5 mmol) in dry acetone (250 ml) were added dropwise and simultaneously over 8 h to a suspension of caesium carbonate (7.5 g, 23 mmol) in dry acetone (1 l) under reflux. 9 The reaction mixture was filtered and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica gel, eluent: chloroform) and recrystallization from acetone to yield 23% of 2 as a colourless solid: mp > 300 ЊC (Found: C, 82.41; H, 5.55.…”

Section: Methodsmentioning

confidence: 99%

“…Host compound 2 was prepared in 23% yield by macrocyclization reaction from 1 and 2,5-dimethoxy-1,3-bis(bromomethyl)benzene under high dilution conditions using Cs 2 CO 3 in acetone as the solvent-base system. 9 Inclusion compounds of 1 were obtained by simple recrystallization from the respective solvent.…”

Section: Synthesismentioning

confidence: 99%

4,4′-(Fluorene-9,9-diyl)diphenol: a new versatile building block for clathrate type and macrocyclic host–guest inclusion

Apel

Nitsche

Beketov

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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published as an Advance Article on the web 5th June 2001 4,4Ј-(Fluorene-9,9-diyl)diphenol ( 1) is demonstrated to be both an effective clathrate host in itself and a useful construction element to form a rigid macrocyclic host compound 2. The X-ray crystal structures of 1 and of its inclusion compounds with acetonitrile (1 : 1) and ethanol (1 : 2) as well as the inclusion compound of 2 with dimethyl sulfoxide (1 : 4) and the mixed-guest inclusion compounds of 2 with 2-picoline, 3-picoline or 4-picoline and acetone (2 : 2 : 1) are reported. Inclusion compounds of 1 with acetonitrile and ethanol are studied by thermal analysis.

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Complexation Behavior of a Highly Preorganized 7,7‐Diphenylnorbornane‐Derived Macrocycle: Towards the Design of Molecular Clocks

Martı́nez

Barcina

Heras

et al. 2003

Chemistry A European J

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The syntheses of two new cyclophane hosts, 4 and 6, are described. The main difference between them is the higher degree of preorganization of 4 as a consequence of the inclusion of the 7,7-diphenylnorbornane (DPN) subunit. The inner cavity of 4 adopts a belt-shaped structure, while 6 has a twisted geometry. In the solid state, the molecules of macrocycle 6 are stacked along an axis to form nanotubular structures. Compounds 4 and 6 form two of the strongest complexes between arene cyclophanes and Ag(+) reported up to date. The silver cation is located inside the cavity of the macrocycles. The stability of 4.Ag(+) is considerably higher than that of 6.Ag(+). The additional stabilization of 4.Ag(+) is attributed to higher preorganization of macrocycle 4. DNMR experiments as well as theoretical calculations carried out with 4.Ag(+) show evidence of Ag(+)-hopping between two different binding sites inside the macrocycle. This phenomenon could be the basis for the design of molecular clocks.

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Structure and kinetics of novel cyclophane inclusion compounds

Cited by 5 publications

References 11 publications

Influence of Highly Preorganised 7,7-Diphenylnorbornane in the Free Energy of Edge-to-Face Aromatic Interactions

Influence of Highly Preorganised 7,7-Diphenylnorbornane in the Free Energy of Edge-to-Face Aromatic Interactions

4,4′-(Fluorene-9,9-diyl)diphenol: a new versatile building block for clathrate type and macrocyclic host–guest inclusion

Complexation Behavior of a Highly Preorganized 7,7‐Diphenylnorbornane‐Derived Macrocycle: Towards the Design of Molecular Clocks

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