The supramolecular chemistry of 1,2,5-chalcogenadiazoles

Cozzolino, Anthony F.; Vargas‐Baca, Ignacio

doi:10.1016/j.jorganchem.2007.02.033

Cited by 54 publications

(45 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[21] Among the different chalcogenide derivatives, benzo-2,1,3-telluradiazoles have certainly attractedt he greatest interest because of their unique ribbon-like self-organization in the solid state (Figure 1a)f ormedt hrough strong N···TeS BIs (2.682(7)-2.720 (7) ). [4,[28][29][30][31] Although of great potential, these molecular systemsh ave remained confined to the fundamentalr esearch because of their thermali nstability and aptitude to undergo hydrolysis under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

“…Considering the experimental evidences and the theoretical studies, strong SBIs can be expected when descending in the chalcogen group, with the Te‐derived compounds establishing the strongest interactions . Among the different chalcogenide derivatives, benzo‐2,1,3‐telluradiazoles have certainly attracted the greatest interest because of their unique ribbon‐like self‐organization in the solid state (Figure a) formed through strong N⋅⋅⋅Te SBIs (2.682(7)–2.720(7) Å) . Although of great potential, these molecular systems have remained confined to the fundamental research because of their thermal instability and aptitude to undergo hydrolysis under ambient conditions.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions

Kremer

Fermi

Biot

et al. 2016

Chemistry A European J

118

112

View full text Add to dashboard Cite

The high-yielding synthesis of 2-substituted benzo-1,3-tellurazoles and benzo-1,3-selenazoles through a dehydrative cyclization reaction has been reported, giving access to a large variety of benzo-1,3-chalcogenazoles. Exceptionally, these aromatic heterocycles proved to be very stable and thus very handy to form controlled solid-state organizations in which wire-like polymeric structures are formed through secondary N⋅⋅⋅Y bonding interactions (SBIs) engaging the chalcogen (Y=Se or Te) and nitrogen atoms. In particular, it has been shown that the recognition properties of the chalcogen centre at the solid state could be programmed by selectively barring one of its σ-holes through a combination of electronic and steric effects exerted by the substituent at the 2-position. As predicted by the electrostatic potential surfaces calculated by quantum chemical modelling, the pyridyl groups revealed to be the stronger chalcogen bonding acceptors, and thus the best ligand candidate for programming the molecular organization at the solid state. In contrast, the thiophenyl group is an unsuitable substituent for establishing SBIs in this molecular system as it gives rise to chalcogen-chalcogen repulsion. The weaker chalcogen donor properties of the Se analogues trigger the formation of feeble N⋅⋅⋅Se contacts, which are manifested in similar solid-state polymers featuring longer nitrogen-chalcogen distances.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions

Kremer

Fermi

Biot

et al. 2016

Chemistry A European J

118

112

View full text Add to dashboard Cite

show abstract

“…The self-assembly behavior of 1,3-benzotellurazoles is somewhat more varied than that of 1,2,5-telluradiazoles, which have long been known known to form molecular ribbons [23][24]. Those carrying isobutyl, phenyl, 2-phenylvinyl, 2-furanyl, 2-thienyl, 2-pyridyl, 3-pyridyl, 4pyridyl, and ferrocenyl substituents in position 2 were previously shown to self-assemble following a wire motif, in which each tellurium atom coordinates with a nitrogen atom on an adjacent tellurazole molecule [5].…”

Section: Discussionmentioning

confidence: 99%

Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles

Smith¹,

Franklin²,

Goutierrez³

et al. 2019

AJHC

View full text Add to dashboard Cite

Synthetic methods have been developed to prepare novel 1,3-benzotellurazoles carrying acylamino and arylamino moieties in position 2, in order to investigate their propensity to self-assemble to supramolecular structures. The targeted compounds were obtained in yields ranging from 44% to 67%, by reacting bis(2-aminophenyl) ditelluride with acyl-and aryl isothiocyanates, respectively, and subsequent reductive cyclization of the resulting thiourea derivatives. Seven novel 1,3benzotellurazole derivatives were prepared: 2-benzoylamino-1,3-benzotellurazole, 2-(4-chlorobenzoylamino)-1,3benzotellurazole, 2-(2-bromobenzoylamino)-1,3-benzotellurazole, 2-(4-bromobenzoylamino)-1,3-benzotellurazole, 2-(4methoxybenzoylamino)-1,3-benzotellurazole, 2-phenylamino-1,3-benzotellurazole, and 2-(4-chlorophenylamino-1,3benzotellurazole. A simplified protocol was employed to synthesize all acyl isothiocyanates needed for their preparation from benzoyl halide derivatives and potassium thiocyanate. The reductive cyclization of the intermediate thioureas was challenging, only the use of hydroxymethanesulfinate in the presence of elemental mercury provided synthetically useful product yields. A mechanism was proposed, consisting of the insertion of mercury into the Te-Te bond, followed by intramolecular nucleophilic attack of the thiocarbonyl moiety by the resulting insertion product. All 2-acylamino-1,3-benzotellurazoles are crystalline solids, which are stable to ambient light, air and moderate heat. A characterization of selected samples by X-ray crystallography indicated that they form dimers in solid state, resulting from hydrogen bonding between the exocyclic and endocyclic nitrogen atoms of two adjacent molecules. This sets them apart from 2-alkyl-and 2-aryl-1,3-benzotellurazoles, which are known to self-assemble into supramolecular wires.

show abstract

“…Another important field dealing with structures characterized by the X-N bond motif is represented by binary chalcogen-nitrogen and ternary S, N, P molecules with intriguing future applications for fingerprint detection, optoelectronic devices, and as hydrogen-storage materials [4]. Finally, taking into account the importance of the supramolecular chemistry, 1,2,5-chalcogenadiazoles are promising building blocks for the development of conductors, optical devices, and self-assembled materials [43][44][45].…”

Section: Introductionmentioning

confidence: 99%

Chalcogen-Nitrogen Bond: Insights into a Key Chemical Motif

et al. 2021

View full text Add to dashboard Cite

Chalcogen-nitrogen chemistry deals with systems in which sulfur, selenium, or tellurium is linked to a nitrogen nucleus. This chemical motif is a key component of different functional structures, ranging from inorganic materials and polymers, to rationally designed catalysts, to bioinspired molecules and enzymes. The formation of a selenium–nitrogen bond, typically occurring upon condensation of an amine and the unstable selenenic acid, often leading to intramolecular cyclizations, and its disruption, mainly promoted by thiols, are rather common events in organic Se-catalyzed processes. In this work, focusing on examples taken from selenium organic chemistry and biochemistry, the selenium–nitrogen bond is described, and its strength and reactivity are quantified using accurate computational methods applied to model molecular systems. The intermediate strength of the Se–N bond, which can be tuned to necessity, gives rise to significant trends when comparing it to the stronger S– and weaker Te–N bonds, reaffirming also in this context the peculiar and valuable role of selenium in chemistry and life.

show abstract

The supramolecular chemistry of 1,2,5-chalcogenadiazoles

Cited by 54 publications

References 18 publications

Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions

Supramolecular Wiring of Benzo‐1,3‐chalcogenazoles through Programmed Chalcogen Bonding Interactions

Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles

Chalcogen-Nitrogen Bond: Insights into a Key Chemical Motif

Contact Info

Product

Resources

About