Isolation and structures of some selenium and tellurium derivatives of 1, 4, 5, 8, 9, 12-hexabromododecahydrotriphenylene as co-crystals of triphenylene

Abstract

The synthesis and characterization of low-valent organoselenium and tellurium derivatives of hexabromododecahydrotriphenylene has been attempted. The reaction of hexabromododecahydrotriphenylene with in situ generated disodium dichalcogenides (Na 2 E 2 ; E = Se, Te) afforded insoluble chalcododecahydrotriphenylene derivatives, 20, 21 respectively. Attempted aromatization of 20 and 21 using DDQ (2, 3-dichloro-5, 6-dicyano-1,4-benzoquinone) as an oxidizing agent afforded the co-crystals. The hexaselenophenyl derivative, 22 and the hexaselenocyanate derivative 23 were synthesized by the reaction of in situ generated sodium arylselenolate/potassium selenocyanate with hexabromododecahydrotriphenylene, respectively. The compounds were characterized by common spectroscopic tools and a few by single crystal x-ray crystallographic studies.

Tuning Magnetic Interactions Between Triphenylene Radicals by Variation of Crystal Packing in Structures with Alkali Metal Counterions

“…In neutral 1 , the C–C bond distances at position e are 1.464(5)–1.470(5) Å . Notably, one of the bonds of 1 ·– at position e is shortened by about 0.03 Å (1.435(7) Å) in 2 and it is further reduced in the CIP complexes 3 – 5 (1.416(3) Å, 1.416(4) Å, 1.425(4) Å, respectively).…”

“…In neutral 1, the C−C bond distances at position e are 1.464(5)−1.470(5) Å. 52 Notably, one of the bonds of 1 •− at position e is shortened by about 0.03 Å (1.435(7) Å) in 2 and it is further reduced in the CIP complexes 3−5 (1.416(3) Å, 1.416(4) Å, 1.425(4) Å, respectively). As also observed in 50 this may be a general indication of the increased electronic density around the specific area of the monoreduced triphenylene core (Table 2).…”

“…The crystal structure of triphenylene (C 18 H 12 , 1) was first reported by Ahmed in 1963, 51 and it was optimized by Prasad in 2014. 52 Since the only prior example of the crystallographically characterized triphenylide-based molecular solid pointed to the importance of cation-π interactions, 50 we explored the effect of different alkali metals on tuning the solidstate structures and properties of the resulting products.…”

Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds: Synthetic Routes, Properties, and Applications

“…in 2014 (Scheme ). These systems were obtained by means of nucleophilic bridging of the saturated hexabromo derivative 177.1 , followed by oxidative aromatization/ring contraction of the triply annulated intermediates 177.2a – b . Unfortunately, the bridges were unselectively cleaved during the oxidative step, and the resulting product mixtures could not be separated without decomposition.…”

“… a Reagents and conditions: (a) Na 2 Se 2 , THF, 24 h, rt; (b) Na 2 Te 2 , THF, 24 h, rt; (c) DDQ, PhCl, reflux 10 h. …”