From four-fold functionalised [3.3]cyclophanes to belt-shaped and multibridged molecules

Breidenbach, Stefan; Harren, Jörg; Neumann, Susanne; Nieger, Martin; Rissanen, Kari; Vögtle, Fritz

doi:10.1039/p19960002061

Cited by 13 publications

(7 citation statements)

References 32 publications

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“…216 Vo ¨gtle studied the crystal structure of complexes of a series of belt-shaped cyclophane 4 (Fig. 18), 217,218 concave macrobicycles 5 219 and broad molecular ribbons composed of biphenyl units 6. 220 They pointed out the stabilizing effect of CH/p bonds in the complexation.…”

Section: Synthetic Macrocyclic Hosts Other Than Calixarenementioning

confidence: 99%

CH/? hydrogen bonds in crystals

Nishio¹

2004

CrystEngComm

1,389

781

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The nature and characteristics of the CH/p interaction are discussed by comparison with other weak molecular forces such as the CH/O and OH/p interaction. The CH/p interaction is a kind of hydrogen bond operating between a soft acid CH and a soft base p-system (double and triple bonds, C 6 and C 5 aromatic rings, heteroaromatics, convex surfaces of fullerenes and nanotubes). The consequences of CH/p hydrogen bonds in supramolecular chemistry are reviewed on grounds of recent crystallographic findings and database analyses. The topics include intramolecular interactions, crystal packing (organic and organometallic compounds), host/ guest complexes (cavity-type inclusion compounds of cyclodextrins and synthetic macrocyclic hosts such as calixarenes, catenanes, rotaxanes and pseudorotaxanes), lattice-inclusion type clathrates (including liquid crystals, porphyrin derivatives, cyclopentadienyl compounds and C 60 fullerenes), enantioselective clathrate formation, catalytic enantioface discriminating reactions and solid-state photoreaction. The implications of the CH/p concept for crystal engineering and drug design are evident.

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Section: Synthetic Macrocyclic Hosts Other Than Calixarenementioning

confidence: 99%

CH/? hydrogen bonds in crystals

Nishio¹

2004

CrystEngComm

1,389

781

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“…2, 295-305 ISSN 0039-7881 © Thieme Stuttgart • New York The smallest intermolecular possibility for macrocyclization to benzene based pseudobeltanes is the cyclization with the p-xylene-bis(tosylamide) 37. The yield of this amide is even 10% higher than the yield of the known durene based tetraamide 18 9 to generate tetrafunctionalized molecular ribbons and genuine belts 9,13,17 derived from these (Scheme 8).…”

Section: Resultsmentioning

confidence: 96%

Linear and Macrocyclic Molecular Thread, Ribbon and Belt Assemblies of Nanometric Scale

Schwierz¹,

Vögtle²

1999

Synthesis

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The hitherto longest molecular thread-belt assemblies 8 , 29 , 32 and 43 based on benzene-connected [3.3]metacyclophane units were prepared by means of a repetitive synthetic method. The preparation of difunctionalized [3.3]metacyclophane units (14 , 22 , 26) succeeded in good yields by an iteration sequence including the cyclization to the cyclophane skeleton and the derivatization of the ester groups. The covalent linkage of the [3.3]metacyclophane belt parts to the thread part leads to higher product yields compared to cyclophane belts only. The final intermolecular macrocyclizations are done by reaction of diamide, dithiol or dibromide functionalized belt fragments to obtain a minimum of single bridged benzene units in the macrocyclic thread-belt assemblies (ÒpseudobeltsÓ).

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“…The common intermediate (6) for both 3 a and 3 b was readily prepared by the reaction of bis(tetraethylammonium) bis(1,3-dithiole-2-thione-4,5-dithiolato)zincate, (TEA) 2 [Zn(dmit) 2 ], and 5 derived by the selective deprotection/realkylation of tetrakis(cyanoethylthio)TTF. Selective deprotection of one cyanoethyl group of 6 with CsOH´H 2 O (1.1 equiv) followed by alkylation with 0.5 equivalents of 1,3-diiodopropane or bis(2-iodoethyl)ether gave 7 in moderate yields, which was subsequently deprotected/realkyated under high-dilution conditions to give the bis-TTF macrocycles with two 1,3-dithiole-2-thione moieties (8). After trans-chalcogenation of 8 into the corresponding ketones (9) by the standard procedure (mercury acetate), the intramolecular coupling reaction, mediated by triethylphosphite, gave the desired multibridged tris-TTF macrocycles 3 in relatively high yields of 61 % and 53 % for 3 a and 3 b, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…Although 4 crystallizes with one chloroform molecule as solvent of crystallization, the solvent molecule lies outside the cavity. [8] Cory ± Pauling ± Koltun (CPK) modeling suggests that our target, tris-TTF macrocycles (3), have rather larger cavities than those of 2 and 4.…”

Section: Introductionmentioning

confidence: 96%

A Flexible Cyclophane: Design, Synthesis, and Structure of a Multibridged Tris-tetrathiafulvalene (TTF) Macrocycle

Takimiya¹,

Thorup

Becher³

2000

Chem. Eur. J.

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The tris-tetrathiafulvalene (TTF) macrocycles 3 with a large end-cavity were effectively synthesized from the readily available tetrakis(cyanoethylthio)TTF by means of a selective deprotection/realkylation sequence followed by an intramolecular coupling reaction. Crystar structure analyses revealed that the neutral molecules include two (3a) or one chloroform molecule (3b) as solvent of crystallization inside the cavity, whereas the I3- salt of 3b, obtained by electrocrystallization, has a molecular structure which is different from that of the neutral molecule in that the cavity has completely collapsed.

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From four-fold functionalised [3.3]cyclophanes to belt-shaped and multibridged molecules

Cited by 13 publications

References 32 publications

CH/? hydrogen bonds in crystals

CH/? hydrogen bonds in crystals

Linear and Macrocyclic Molecular Thread, Ribbon and Belt Assemblies of Nanometric Scale

A Flexible Cyclophane: Design, Synthesis, and Structure of a Multibridged Tris-tetrathiafulvalene (TTF) Macrocycle

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