Tribenzotriquinacen: eine vielseitige Synthese und <i>C</i><sub>3</sub>‐chirale Plattformen

Μαρκόπουλος, Γεώργιος; Henneicke, Lars; Shen, Jun; Jones, Peter G.; Hopf, Henning

doi:10.1002/ange.201207220

Cited by 35 publications

(13 citation statements)

References 51 publications

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“…Whereas the higher homologue (3) forms large colorless crystals with m.p. 243-245 8C, [7] the lower homologue (2) starts to crystallize from hot solvents, such as toluene or xylenes, thus forming extremely thin and long needles that melt at about 390 8C, [8,9] that is, almost 150 8C higher than compound 3. With the X-ray crystal structure of compound 3 in hand, [10] it was natural to assume that the solid-state aggregation of the lower homologue (2) would display a similar (but much tighter) crystal packing because of the absence of the apical methyl group.…”

Section: Resultsmentioning

confidence: 99%

“…[31,32] The energy cutoff for the plane wave set was set at 1000 eV to achieve energy convergence. (17) C4b-C12d-C8b 107.30 (9) 106.61(10) C4c-C4b-C12d 104.70 (9) 105.12 (9) C4bÀC4c 1.5172 (16) (11) [a] Libration corrections [25] of +0.001 and +0.002 to all CÀC bond lengths were calculated for compounds 2 and 3, respectively. All monomer energies were calculated at the G point in a large unit cell of size 20 20 10 3 .…”

Section: Structural Optimization-computational Detailsmentioning

confidence: 99%

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Unidirectional Molecular Stacking of Tribenzotriquinacenes in the Solid State: A Combined X‐ray and Theoretical Study

Brandenburg

Grimme

Jones

et al. 2013

Chemistry A European J

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A combined X-ray diffraction and theoretical study of the solid-state molecular and crystal structures of tribenzotriquinacene (TBTQ, 2) and its centro-methyl derivative (3) is presented. The molecular structure of the parent hydrocarbon displays C3v symmetry and the three indane wings adopt mutually orthogonal orientations, similar to the case in its previously reported methyl derivative (3). Also similarly to the latter structure, the bowl-shaped molecules of compound 2 form infinite molecular stacks with perfectly axial, face-to-back (convex-concave) packing and with parallel and unidirectional orientation of the stacks. The experimentally determined intra-stack molecular distance is 4.75 Å for compound 2 and 5.95 Å for compound 3. Whereas the molecules of compound 2 show a slight alternating rotation (±6°) about the common axis of each stack, those of compound 3 show perfect translational symmetry within the stacks. We used dispersion-corrected density functional theory to compute the crystal structures of tribenzotriquinacenes 2 and 3. The London dispersion correction was crucial for obtaining an accurate description of the crystallization of both analyzed systems and the calculated results agreed excellently with the experimental measurements. We also obtained reasonable sublimation energies for both compounds. In addition, the geometries and dimerization energies of oligomeric stacks of compound 2 were computed and showed smooth convergence to the properties of the infinite polymeric stack.

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Section: Resultsmentioning

confidence: 99%

Section: Structural Optimization-computational Detailsmentioning

confidence: 99%

Unidirectional Molecular Stacking of Tribenzotriquinacenes in the Solid State: A Combined X‐ray and Theoretical Study

Brandenburg

Grimme

Jones

et al. 2013

Chemistry A European J

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“…Tribenzotriquinacenes, such as the centro ‐methyl TBTQ derivative 1 , are highly versatile building blocks for the construction of extended polyaromatic structures with extended π‐electron chromophores and of large covalently and noncovalently bound host molecules . Both achiral and chiral congeners with broadly varied functionalization pattern have been developed and used for the extension of the three orthogonally oriented wings of the TBTQ framework .…”

Section: Introductionmentioning

confidence: 99%

Combining Stereoselective Enzyme Catalysis with Chirality‐Assisted Synthesis in Tribenzotriquinacene Chemistry

et al. 2018

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The stereoselective synthesis of enantiomerically pure single‐wing‐functionalized tribenzotriquinacenes using the enzyme CAL‐B was successfully extended towards operating on a multi‐gram scale. Based on the (P)‐tribenzotriquinacene‐2‐carbaldehyde (P)‐6 obtained in >99 % ee, the hitherto unknown (P)‐2‐hydroxy‐ and (M)‐2‐hydroxy‐3‐iodo‐TBTQ derivatives (P)‐9 and (M)‐10 were prepared in optically pure form. The bowl‐shaped ortho‐iodophenol (M)‐10 was subjected to a twofold crosswise Ullmann‐type condensation to give, albeit in low yield (10 %), the 1,4‐dioxine 5, in which two TBTQ bowls are fused exclusively in a syn‐bi‐concave orientation, thus demonstrating a new example for a chirality‐assisted synthesis. The corresponding Ullmann condensation of the racemic TBTQ‐ortho‐iodophenol rac‐10 furnished the respective anti‐bis‐TBTQ‐dioxine 11 as the major diastereomer together with the syn‐isomer 5 in the same total yield and in a 11/5 ratio of at least 4. The two diastereomeric bis‐TBTQ‐dioxines show minor but significant differences in most of the characteristic 1H‐NMR chemical shifts. The solid‐state structure of the syn‐dimer 5, determined by X‐ray diffraction, was found to consist of pairs of host–guest complexes, [5·CH2Cl2]2, with pronounced face‐to‐face orientation of the bi‐concave host molecules.

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“…[13] In the present work, three acene units have been incorporated into the three-dimensional framework of tribenzotriquinacene (TBTQ, 1). [14][15][16] This polycyclic hydrocarbon belonging to the centropolyindane family [17] has a conformationally rigid and highly symmetrical (C 3v ) carbon framework consisting of three indane wings oriented orthogonally to each other (A, Figure 1). [17][18][19] Owing to this unique spatial arrangement and the bowl-shaped architecture of 1, we expected increased solubility of threefold aceno-annellated triquinacenes, such as B, which would contribute a new facet to the field.…”

Section: Introductionmentioning

confidence: 99%

Tris(tetraceno)triquinacenes: Synthesis and Photophysical Properties of Threefold Linearly Extended Tribenzotriquinacenes

Mughal

Eberhard

Kuck

2013

Chemistry A European J

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The linear extension of the rigid, C(3v)-symmetrical carbon framework of tribenzotriquinacene (TBTQ) along its three wings is reported. The key step of the extension procedure consists of a Diels-Alder reaction of three ortho-quinodimethane units generated in situ at the triquinacene core. The use of 1,4-naphthoquinone provides a facile and particularly efficient access to tris(tetraceno)-annellated triquinacenes. The steady-state photophysical properties of these new oligotetracenes bearing three mutually orthogonal chomophores are determined and analyzed by DFT calculations.

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Tribenzotriquinacen: eine vielseitige Synthese und C₃‐chirale Plattformen

Cited by 35 publications

References 51 publications

Unidirectional Molecular Stacking of Tribenzotriquinacenes in the Solid State: A Combined X‐ray and Theoretical Study

Unidirectional Molecular Stacking of Tribenzotriquinacenes in the Solid State: A Combined X‐ray and Theoretical Study

Combining Stereoselective Enzyme Catalysis with Chirality‐Assisted Synthesis in Tribenzotriquinacene Chemistry

Tris(tetraceno)triquinacenes: Synthesis and Photophysical Properties of Threefold Linearly Extended Tribenzotriquinacenes

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Tribenzotriquinacen: eine vielseitige Synthese und C3‐chirale Plattformen

Cited by 35 publications

References 51 publications

Unidirectional Molecular Stacking of Tribenzotriquinacenes in the Solid State: A Combined X‐ray and Theoretical Study

Unidirectional Molecular Stacking of Tribenzotriquinacenes in the Solid State: A Combined X‐ray and Theoretical Study

Combining Stereoselective Enzyme Catalysis with Chirality‐Assisted Synthesis in Tribenzotriquinacene Chemistry

Tris(tetraceno)triquinacenes: Synthesis and Photophysical Properties of Threefold Linearly Extended Tribenzotriquinacenes

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Tribenzotriquinacen: eine vielseitige Synthese und C₃‐chirale Plattformen