An aza-cyclophane stacked in racemic columnar assemblies: whole-molecule disorder in a two-dimensional solid solution

Zeller, Mat­thias; Lutz, Marlon R.; Becker, Daniel P.

doi:10.1107/s0108768109002134

Cited by 6 publications

(6 citation statements)

References 18 publications

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“…[1][2][3][4] As part of our research program directed toward the synthesis and application of apex-modified CTV derivatives [5][6][7] with unique material properties and applications involving host-guest chemistry 8 we recently reported the synthesis of the new triaza orthocyclophane 2a 9 ( Figure 1) which was alkylated to give the N,N',N''-trimethyl derivative 2b. Following a 6-step linear sequence to obtain the precursor 3a (Scheme 1), two mechanistically different approaches were examined in order to obtain the final desired triazacyclophane 2a (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

et al. 2013

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Treatment of chlorotriaryl derivatives 3a and 3d or fluorotriaryl derivatives 3b and 3e with potassium diisopropylamide afforded alkyl-shifted phenazine derivatives 5a/5b, rather than the expected 9-membered triaza orthocyclophane 2a. The phenazine derivatives were isolated in 78-98% yield depending on the halogen and alkyl group present. In the absence of the halogen (chloro or fluoro), the apparent alkyl shift proceeds more slowly and cannot proceed via, the intermediacy of the aryne

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Section: Introductionmentioning

confidence: 99%

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

et al. 2013

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“…Part of our research program is focused on the construction of apex-modified derivatives [15][16][17] of the trimeric crown-shaped (bowl-shaped) [1.1.1]orthocyclophane cyclotriveratrylene 1 (CTV, Figure 2) 18 with applications in host-guest chemistry. 19 Trans-annular rearrangements are known to occur when attempting to oxidize CTV-5,10-dione 1c to the corresponding triketone which leads to rearrangement to the spiro derivative 2, 20, 21 and we have observed a trans-annular electrophilic aromatic addition or substitution cascade following a Beckmann rearrangement reaction on a related system.…”

Section: Resultsmentioning

confidence: 99%

Rearrangement of Cyclotriveratrylene (CTV) Diketone: 9,10-Diarylanthracenes with OLED Applications

et al. 2012

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Electroluminescent 9,10-diaryl anthracenes have been shown to be promising host and hole-transporting materials in organic electroluminescence due to their high thermal stability, electrochemical reversibility and wide band gap useful for organic light emitting diodes (OLEDs), especially blue OLEDs. Oxidation of cyclotriveratrylene (CTV) to the corresponding diketone and subsequent bromination resulted in an unexpected rearrangement to a highly functionalized 9-aryl-10-bromoanthracene derivative, which was employed in Suzuki couplings to synthesize a series of 9,10-diaryl compounds that are structural analogs of anthracene derivatives used in the preparation of OLEDs, but are more highly functionalized, including electron-donating methoxy groups in addition to substitution by a carboxylic acid moiety. The UV/fluorescence solution spectra show strong emissions at a 446 nm, 438 nm and 479 nm, respectively, for the anthracene 10-phenyl, 10-naphthyl and 10-pyrenyl adducts containing a benzoic acid functional group, whereas the analogs bearing the hydroxymethylene moiety from reduction of the benzoic acid to the corresponding alcohols gave much shorter emission wavelengths of 408 nm, 417 nm, and 476 nm, respectively, and had somewhat higher quantum yields, suggesting they are better candidates for OLED applications.

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“…Related C16-centroid C9B-C14B and C16Bcentroid C9-C14 distances of $ 3.5 Å are given in Table 3A of the supplementary material. Zeller et al (2009) shows a similar C Me -aromatic centroid intermolecular distance, 3.50 Å .…”

Section: Packing Analysis For (Iiia) (Iiib) (Iva) (Va) and (Viia)mentioning

confidence: 90%

Thermal motion of tert-butyl groups III. tert-Butyl substituents in aromatic hydrocarbons, the view from the bottom of the well

Frey

Khan

Knobler

et al. 2010

Acta Crystallogr Sect B

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The rigidity of the tert-butyl group (TBG) as a substituent in aromatic hydrocarbons is investigated, with a modified Hirshfeld test of anisotropic displacement parameters (ADPs) as a primary criterion. Four new structures are analyzed, along with low-temperature studies of a previously published crowded supermesityl dimer; three of the five structures meet the primary test. Most of the TBGs meet the Hirshfeld test at 100 K, and the ADPs are improved by omitting low-order data in the final refinement. The three most precise structures yield a wide variation in libration amplitudes (and in estimated rotation barriers) for 13 unique TBGs. A similar range of values is found in analyses of structures in the Cambridge Crystallographic Database. The libration amplitudes are calculated with the program THMA14C, with each TBG as an attached rigid group (ARG). Packing analysis suggests that large ADPs, especially for some individual TBG methyl groups, correspond to voids in the crystal. Published barriers to TBG reorientation, determined by solid-state NMR spin-lattice relaxation methods, for six related crystalline compounds are compared with barriers calculated from their crystal structure data.

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An aza-cyclophane stacked in racemic columnar assemblies: whole-molecule disorder in a two-dimensional solid solution

Cited by 6 publications

References 18 publications

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

Rearrangement of Cyclotriveratrylene (CTV) Diketone: 9,10-Diarylanthracenes with OLED Applications

Thermal motion of tert-butyl groups III. tert-Butyl substituents in aromatic hydrocarbons, the view from the bottom of the well

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