1,9-Disubstituted triptycenes: an excellent probe for weak molecular interactions

Ōki, Michinori

doi:10.1021/ar00179a001

Cited by 100 publications

(40 citation statements)

References 40 publications

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“…[36] Seit den bahnbrechenden Arbeiten von Ō ki [67] haben sich Triptycenderivate [68] [70] Analog zu deren früherem 1,8-Diarylnaphthalin-Modellsystem [71] nahm die Rotationsbarriere (DG°) in beiden Serien mit zunehmend elektronenziehenden Substituenten zu. Eine ausgezeichnete Korrelation mit den Hammett-Parametern s p wurde gefunden, was die Rolle der polaren p-Effekte unterstreicht.…”

Section: Modellstudienunclassified

Aromatische Ringe in chemischer und biologischer Erkennung: Energien und Strukturen

2011

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Dieser Aufsatz beschreibt Phänomene der molekularen Erkennung von aromatischen Ringen in chemischen und biologischen Systemen in einem multidimensionalen Ansatz. Neue Ergebnisse aus der Wirt‐Gast‐Chemie, biologischen Affinitätsassays und Biostrukturanalysen, Datenbanksuchen in der Cambridge Structural Database (CSD) und der Protein Data Bank (PDB) und hochentwickelten Rechnungen, die seit dem Erscheinen eines früheren Aufsatzes in 2003 veröffentlicht wurden, sind hier zusammengefasst. Die Themen Aren‐Aren‐, Perfluoraren‐Aren‐, Schwefel‐Aren‐, Kation‐π‐ und Anion‐π‐Wechselwirkungen sowie Wasserstoffbrücken zu aromatischen Systemen werden behandelt. Das gewonnene Wissen kommt besonders der strukturbasierten Hit‐zur‐Leitstruktur‐Entwicklung und der Leitstrukturoptimierung sowohl in der pharmazeutischen als auch in der Pflanzenschutzindustrie zugute. Zudem erleichtert es die Entwicklung neuer Materialien und supramolekularer Systeme und soll zu weiteren Anwendungen von Wechselwirkungen mit aromatischen Ringen zur Kontrolle des stereochemischen Verlaufs chemischer Umsetzungen inspirieren.

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Section: Modellstudienunclassified

Aromatische Ringe in chemischer und biologischer Erkennung: Energien und Strukturen

2011

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“…5 . Although many examples of restricted rotation of a single bond are known, [23][24][25][26][27][28][29][30][31][32][33] this represents a new type of restricted rotation. A direct 180°rotation around CH 2 -C ipso must surmount a much higher activation enthalpy than the observed value.…”

Section: Discussionmentioning

confidence: 99%

1H-NMR Study of Ternary Platinum(II) Complexes with N-(1-Naphtyl)methyl-1,2-ethanediamine or N-(9-Anthrylmethyl)-1,2-ethanediamine and Bipyridine or Phenanthroline and Restricted Single Bond Rotation Due to Aromatic-Aromatic Ring Interaction

Yamakawa

Sumimoto

Matsumoto

et al. 2008

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…[9]; the deuterated compound, Tp-GeD 3 , was obtained by reducing Tp-GeCl 3 with LiAlD 4 . Single crystals have been grown by slow evaporation of a solution in a mixture hexane/ether (9/1), in the dark and under a nitrogen flow.…”

Section: Methodsmentioning

confidence: 99%

“…In this context, considerable effort has been focused on triptycene derivatives which represent one of the simplest molecular gears [2,3]. In these systems, rotatory motions around the Tp -X (Tp: triptycene) bond are, of course, of crucial importance and are generally investigated using NMR spectroscopy [4][5][6]. However, this method can be hardly used when X is a paramagnetic moiety, and we have the anisotropy of the g-tensor and can be efficiently analyzed even in the absence of any hyperfine coupling with A.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular motion in the triptycenegermanyl radical: single crystal EPR study at variable temperature and DFT calculations

Brynda

Dutan

Berclaz

et al. 2003

Journal of Physics and Chemistry of Solids

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X-irradiation of single crystals of Tp-GeH 3 (Tp: triptycene) led to the trapping of the radical Tpz GeH 2 . The angular variations of the resulting EPR spectra were recorded at 300 and 77 K. The drastic temperature dependence of the spectra was caused by both a strong anisotropy of the g-tensor and a rotation of the z GeH 2 moiety around the C-Ge bond. The determination of the EPR tensors as well as the analysis of this motion required to take the presence of disorder in the crystal into account. In accordance with DFT calculations, Tpz GeH 2 is shown to be pyramidal and to adopt, in its lowest energy structure, a staggered conformation. Rotation around the C-GeH 2 bond is blocked at 90 K and is almost free above 110 K. The experimental barrier, obtained after simulation of the EPR spectra as a function of the rotational correlation time, is equal to 1.3 kcal mol 21, which is slightly inferior to the barrier calculated by DFT (3.6 kcal mol 21 ). Calculations performed on Tp -CH 3 , Tp -GeH 3 and Tpz GeH 2 show that the rotation barrier DE rot around the C-Ge bond drastically decreases by passing from the germane precursor to the germanyl radical and that DE rot increases by passing from the germane to its carbon analogous. Structural parameters involved in these barrier differences are examined. q

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1,9-Disubstituted triptycenes: an excellent probe for weak molecular interactions

Cited by 100 publications

References 40 publications

Aromatische Ringe in chemischer und biologischer Erkennung: Energien und Strukturen

Aromatische Ringe in chemischer und biologischer Erkennung: Energien und Strukturen

1H-NMR Study of Ternary Platinum(II) Complexes with N-(1-Naphtyl)methyl-1,2-ethanediamine or N-(9-Anthrylmethyl)-1,2-ethanediamine and Bipyridine or Phenanthroline and Restricted Single Bond Rotation Due to Aromatic-Aromatic Ring Interaction

Intramolecular motion in the triptycenegermanyl radical: single crystal EPR study at variable temperature and DFT calculations

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