Self-Assembled Trigonal Prismatic Altitudinal Rotors with Triptycene Paddle Wheels

Caskey, Douglas C.; Wang, Bing; Zheng, Xiaolai; Michl, Josef

doi:10.1135/cccc20051970

Cited by 21 publications

(39 citation statements)

References 29 publications

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“…Solvents were removed under reduced pressure, and column chromatography on silica gel (hexane/CH 2 Cl 2 = 4:1) gave 10 as a white crystalline solid (465 mg, 1.433 mmol, 98%) 3280, 3083, 3032, 2963, 2914, 2877, 2219, 2108, 1611, 1507, 1493, 1478, 1463, 1448, 1394, 1364, 1345, 1268, 1251, 1202, 1113, 1029, 1014, 1003, 966, 950, 924, 852, 821, 764, 748, 742, 724, 687 9,10-Diethynyltriptycene (12). 33 To an ice-cold and well stirred solution of 14 (7.589 g, 16.988 mmol) in wet THF (40 mL , which is in agreement with the literature. 33 9,10-Bis(trimethylsilylethynyl)anthracene (13).…”

Section: The Journal Of Organic Chemistrymentioning

confidence: 99%

Arrays of Molecular Rotors with Triptycene Stoppers: Surface Inclusion in Hexagonal Tris(o-phenylenedioxy)cyclotriphosphazene

Kaleta

Dron²,

Zhao³

et al. 2015

J. Org. Chem.

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A new generation of rod-shaped dipolar molecular rotors designed for controlled insertion into channel arrays in the surface of hexagonal tris(o-phenylenedioxy)cyclotriphosphazene (TPP) has been designed and synthesized. Triptycene is used as a stopper intended to prevent complete insertion, forcing the formation of a surface inclusion. Two widely separated (13)C NMR markers are present in the shaft for monitoring the degree of insertion. The structure of the two-dimensional rotor arrays contained in these surface inclusions was examined by solid-state NMR and X-ray powder diffraction. The NMR markers and the triptycene stopper functioned as designed, but half of the guest molecules were not inserted as deeply into the TPP channels as the other half. As a result, the dipolar rotators were distributed equally in two planes parallel to the crystal surface instead of being located in a single plane as would be required for ferroelectricity. Dielectric spectroscopy revealed rotational barriers of ∼4 kcal/mol but no ferroelectric behavior.

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Section: The Journal Of Organic Chemistrymentioning

confidence: 99%

Arrays of Molecular Rotors with Triptycene Stoppers: Surface Inclusion in Hexagonal Tris(o-phenylenedioxy)cyclotriphosphazene

Kaleta

Dron²,

Zhao³

et al. 2015

J. Org. Chem.

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“…42,43 Numerous chemical and biological systems 23,24,44,45,46,47,48 have been studied with this method, including our nanoscopic dodecahedra. 20 The present results are summarized in Table 1.…”

Section: Diffusion Constant Determinationmentioning

confidence: 99%

“…20 These are highly symmetrical species composed of building blocks that define some or all of their edges. Lower symmetry assemblies, for example trigonal 21,22,23,24 and tetragonal 22,23 prisms, are less common and are more easily approached using face-directed techniques in which component linkers span the faces of the desired aggregate. Varying the component dimensions then alters the size and shape of the final assembly.…”

Section: Introductionmentioning

confidence: 99%

Coordination-Driven Face-Directed Self-Assembly of Trigonal Prisms. Face-Based Conformational Chirality

et al. 2008

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The coordination-driven self-assembly of four different trigonal prisms from three equivalents of one of four different tetrapyridyl star connectors and six equivalents of a platinum linker dication in nitromethane is presented. This face-directed approach affords high yield without template assistance. The prisms have been characterized by multinuclear and DOSY NMR and dual ESI-FT-ICR mass spectrometry. The use of a conformationally chiral star connector leads to a conformationally chiral prism when connector arm ends attached to a vertex have a strongly correlated twist sense and chirality is communicated across polyhedral faces, edges and vertices. Molecular mechanics results suggest that in the smallest prism 3d collective effects dominate and the all-P and all-M conformers are strongly favored. NMR data prove that the two edges of the pyridine rings in the triflate salts of 3a -3d are distinct. An Eyring plot of rates obtained from lineshape analysis and 1-D EXCHSY NMR yields an activation enthalpy ΔH ‡ of ∼12 kcal/mol and activation entropy ΔS ‡ of ∼-15 cal/mol.K for the edge interconversion process, compatible with pyridine rotation around the Pt-N bond. For 3c, this behavior is observed only up to ∼318 K. At higher temperatures, the Eyring plot is again linear but follows a very different straight line, with ΔH ‡ of ∼35 kcal/mol and ΔS ‡ of ∼60 cal/mol.K. This highly unusual result is further investigated and discussed in the following companion paper.

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“…The assigned cyclic structure follows from the absence of any 1 H NMR signal that could be assigned to a non-coordinated terminus of 7 and the absence of any 31 P NMR signal attributable to an environment found in the starting nitrato version of 1. 24 However, any larger macrocycle formed from the same components would exhibit the same NMR spectra. To determine the actual size of the molecule, we used electrospray ionization/ion mobility spectrometry (ESI-IMS).…”

Section: Resultsmentioning

confidence: 99%

Mechanical vs Electronic Strain: Oval-Shaped Alkynyl-Pt(II)-Phosphine Macrocycles

et al. 2019

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Self-Assembled Trigonal Prismatic Altitudinal Rotors with Triptycene Paddle Wheels

Cited by 21 publications

References 29 publications

Arrays of Molecular Rotors with Triptycene Stoppers: Surface Inclusion in Hexagonal Tris(o-phenylenedioxy)cyclotriphosphazene

Arrays of Molecular Rotors with Triptycene Stoppers: Surface Inclusion in Hexagonal Tris(o-phenylenedioxy)cyclotriphosphazene

Coordination-Driven Face-Directed Self-Assembly of Trigonal Prisms. Face-Based Conformational Chirality

Mechanical vs Electronic Strain: Oval-Shaped Alkynyl-Pt(II)-Phosphine Macrocycles

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