Chalcogen‐Bonding Interactions in Telluroether Heterocycles [Te(CH₂)_m]_n(n=1–4;m=3–7)

Abstract

The Te•••Te secondary bondingi nteractions (SBIs) in solid cyclic telluroethers were explored by preparinga nd structurally characterizing as eries of [Te(CH 2) m ] n (n = 1-4; m = 3-7) species. The SBIs in 1,7-Te 2 (CH 2) 10 ,1 ,8-Te 2 (CH 2) 12 , 1,5,9-Te 3 (CH 2) 9 ,1 ,8,15-Te 3 (CH 2) 18 ,1 ,7,13,19-Te 4 (CH 2) 20 , 1,8,15,22-Te 4 (CH 2) 24 and1 ,9,17,25-Te 4 (CH 2) 28 lead to tubular packing of the molecules, as has been observed previously for related thio-and selenoether rings. The nature of the in-termolecular interactions wase xploredb ys olid-state PBE0-D3/pob-TZVP calculations involving periodic boundary conditions. The molecular packingi n1 ,7,13,19-Te 4 (CH 2) 20 , 1,8,15,22-Te 4 (CH 2) 24 and 1,9,17,25-Te 4 (CH 2) 28 forms infinite shafts. The electron densities at bond critical points indicate an arrow range of Te •••Te bond orders of 0.12-0.14. Thef ormation of the shafts can be rationalized by frontier orbital overlap and charge transfer.

Quantum chemistry simulations in an undergraduate project: tellurophenes as narrow bandgap semiconductor materials

“…These more favourable properties may be attributed to numerous factors related to the electronic structure, the decreased electronegativity, and bonding polarisation behaviour of tellurium in such conjugated organic molecules [32]. As a caveat of note, the intermolecular interactions between Te atoms, which are notionally stronger than those between Se and S atoms, may further influence variations in properties beyond the intramolecular scope of the study here [33,56].…”

Formation, Characterization, and Bonding of cis- and trans-[PtCl2{Te(CH2)6}2], cis-trans-[Pt3Cl6{Te(CH2)6}4], and cis-trans-[Pt4Cl8{Te(CH2)6}4]: Experimental and DFT Study

“…This is also reflected by the small values of ρ (0.061-0.074 e Å −3 ) and DI (0.06-0.10). They can be compared to the intermolecular Te•••Te chalcogen bonds in solid macrocyclic telluroethers and are of the same order of magnitude [29]. The relative strengths of the Pt•••Pt and Te•••Cl interactions can be qualitatively estimated using E int calculated from V b [63], although some caution should be exercised when drawing conclusions, as the reliability of the relationship has been questioned [64].…”

“…The information on cyclic saturated telluroethers is sparse compared to related thioethers and selenoethers. While the preparation of cyclic Te(CH 2 ) 4 [26], Te(CH 2 ) 5 [27], and 1,5,9-Te 3 (CH 2 ) 9 [28] has been known for a long time, it is only recently that the crystal structures and bonding in some [Te(CH 2 ) m ] n (n = 1-4, m = 3-7) [29] have been discussed. The coordination chemistry of the cyclic telluroethers is also little studied with only [MCl 2 {Te(CH 2 ) 4 } 2 ] (M = Pd, Pt) [30], [PtCl 2 {Te(CH 2 ) 4 O} 2 ] [31], [MCl 2 {Te 2 O 4 (CH 2 ) 12 }] (M = Pd.…”

“…Pt) [32], [Rh 2 (η 5 -C 5 H 5 ) 2 (CO)(µ-η 1 : η 1 -CF 3 C 2 CF 3 ){Te(CH 2 ) 4 }] [33], and [Ag{TeS 2 (CH 2 ) 8 }] n [BF 4 ] n [34] being either structurally or spectroscopically characterized. The current contribution is the continuation of our systematic investigation of the synthesis of the series of telluroether heterocycles [Te(CH 2 ) m ] n (n = 1-4; m = 3-7) [29] and the coordination complexes of telluroethers (see refs. [35][36][37][38][39] for some recent publications).…”

“…Monotelluroethers Te(CH 2 ) m are liquid in ambient conditions, but species with higher Te contents are solid. The molecular structures and the packing of seven macrocyclic aliphatic telluroethers have been explored [29]. Te(CH 2 ) 6 was one of the monotelluroethers that was synthesized and characterized through NMR spectroscopy, but since it is a liquid at room temperature with a low melting point, its crystal structure determination could not be carried out.…”