Supramolecular Organization Based on van der Waals Forces: Syntheses and Solid State Structures of Isomeric [6.6]Cyclophanes with 2,5‐Diselenahex‐3‐yne Bridges

Lari, Alberth; Gleiter, Rolf; Röminger, Frank

doi:10.1002/ejoc.200900106

Cited by 30 publications

(24 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The chains between the rigid E-CC-E units in the cycles can be varied by including other firm units. We mention here solid state structures of isomeric [6.6]cyclophanes with 2,5-diselenahex-3-yne bridges . In Scheme we summarize preparations of the o -, m -, and p -[6.6]cyclophanes 51a to 51c .…”

Section: Noncovalent Chalcogen–chalcogen Interactions: Experimental R...mentioning

confidence: 89%

From Noncovalent Chalcogen–Chalcogen Interactions to Supramolecular Aggregates: Experiments and Calculations

et al. 2018

Self Cite

View full text Add to dashboard Cite

This review considers noncovalent bonds between divalent chalcogen centers. In the first part we present X-ray data taken from the solid state structures of dimethyl- and diphenyl-dichalcogenides as well as oligoalkynes kept by alkyl-sulfur, -selenium, and -tellurium groups. Furthermore, we analyzed the solid state structures of medium sized (12-24 ring size) selenium coronands and medium to large rings with alkyne and alkene units between two chalcogen centers. The crystal structures of the cyclic structures revealed columnar stacks with close contacts between neighboring rings via noncovalent interactions between the chalcogen centers. To get larger space within the cavities, rings with diyne units between the chalcogen centers were used. These molecules showed channel-like structures in the solid state. The flexibility of the rings permits inclusion of guest molecules such as five-membered heterocycles and aromatic six-membered rings. In the second part we discuss the results of quantum chemical calculations. To treat properly the noncovalent bonding between chalcogens, we use diffuse augmented split valence basis sets in combination with electron correlation methods. Our model substances were 16 dimers consisting of two Me-X-Me (X = O, S, Se, Te) pairs and dimers of Me-X-Me/Me-X-CN (X = O, S, Se, Te) pairs. The calculations show the anticipated increase of the interaction energy from (Me-O-Me) (-2.15 kcal/mol) to (Me-O-Me/Me-Te-CN) (-6.59 kcal/mol). An analysis by the NBO method reveals that in the case of the chalcogen centers O and S the hydrogen bridges between the molecules dominate. However, in the case of Se and Te the major bonding between the pairs originates from dispersion forces between the chalcogen centers. It varies between -1.7 and -4.0 kcal/mol.

show abstract

Section: Noncovalent Chalcogen–chalcogen Interactions: Experimental R...mentioning

confidence: 89%

From Noncovalent Chalcogen–Chalcogen Interactions to Supramolecular Aggregates: Experiments and Calculations

et al. 2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…Less frequent in the literature are discrete aggregates of a few molecular units self-assembled by this type of interactions. Supramolecular macrocycles have been observed in the crystal structures of triiodo-1-methyl-imidazole, dichalcogena alkynes, − 2-(iodoethynyl)pyridines, , and 1,2-tellurazole 2-oxides ( 1 and 2 in Chart ). − However, the latter are the only systems whose aggregates have been demonstrated to persist in solution.…”

Section: Introductionmentioning

confidence: 99%

Iso-Tellurazolium-N-Phenoxides: A Family of Te···O Chalcogen-Bonding Supramolecular Building Blocks

Tomassetti

Britten

et al. 2021

Inorg. Chem.

View full text Add to dashboard Cite

Formal substitution of the oxygen atom of an isotellurazole N-oxide with deprotonated (ortho, meta, and para)hydroxyphenyl groups generated molecules that readily aggregate through Te•••O chalcogen bonding (ChB) interactions. The molecules undergo autoassociation in solution, as shown by variable temperature (VT) 1 H NMR experiments and paralleling the behavior of iso-tellurazole N-oxides. Judicious adjustment of crystallization conditions enabled the isolation of either polymeric or macrocyclic aggregates. Among the latter, the ortho compound assembled a calixarene-like trimer, while the para isomer built a macrocyclic tetramer akin to a molecular square. The Te•••O ChB distances in these structures range from 2.13 to 2.17 Å, comparable to those in the structures of iso-tellurazole N-oxides. DFT calculations estimate that the corresponding Te•••O ChB energies are between −122 and −195 kJ mol −1 in model dimers and suggest that macrocyclic aggregation enhances these interactions.

show abstract

“…The potential of chalcogen-centered interactions in supramolecular chemistry is illustrated by two well-studied molecular families: the dichalcogena alkynes, which consistently crystalize in tubular structures assembled by chalcogen–chalcogen interactions 38 39 40 , and the 1,2,5-chalcogenadiazoles, in which two pairs of antiparallel chalcogen–nitrogen interactions per molecule tend to build infinite ribbons. The latter structures are of interest because of their charge transport properties 41 and, through moderate steric repulsion, can be distorted to induce non-linear optical properties or chromotropism 42 43 44 .…”

mentioning

confidence: 99%

Supramolecular macrocycles reversibly assembled by Te…O chalcogen bonding

et al. 2016

View full text Add to dashboard Cite

Organic molecules with heavy main-group elements frequently form supramolecular links to electron-rich centres. One particular case of such interactions is halogen bonding. Most studies of this phenomenon have been concerned with either dimers or infinitely extended structures (polymers and lattices) but well-defined cyclic structures remain elusive. Here we present oligomeric aggregates of heterocycles that are linked by chalcogen-centered interactions and behave as genuine macrocyclic species. The molecules of 3-methyl-5-phenyl-1,2-tellurazole 2-oxide assemble a variety of supramolecular aggregates that includes cyclic tetramers and hexamers, as well as a helical polymer. In all these aggregates, the building blocks are connected by Te…O–N bridges. Nuclear magnetic resonance spectroscopic experiments demonstrate that the two types of annular aggregates are persistent in solution. These self-assembled structures form coordination complexes with transition-metal ions, act as fullerene receptors and host small molecules in a crystal.

show abstract

Supramolecular Organization Based on van der Waals Forces: Syntheses and Solid State Structures of Isomeric [6.6]Cyclophanes with 2,5‐Diselenahex‐3‐yne Bridges

Cited by 30 publications

References 25 publications

From Noncovalent Chalcogen–Chalcogen Interactions to Supramolecular Aggregates: Experiments and Calculations

From Noncovalent Chalcogen–Chalcogen Interactions to Supramolecular Aggregates: Experiments and Calculations

Iso-Tellurazolium-N-Phenoxides: A Family of Te···O Chalcogen-Bonding Supramolecular Building Blocks

Supramolecular macrocycles reversibly assembled by Te…O chalcogen bonding

Contact Info

Product

Resources

About