Abstract

The Te⋅⋅⋅Te secondary bonding interactions (SBIs) in solid cyclic telluroethers were explored by preparing and structurally characterizing a series of [Te(CH₂)ₘ]ₙ (n=1–4; m=3–7) species. The SBIs in 1,7‐Te₂(CH₂)₁₀, 1,8‐Te₂(CH₂)₁₂, 1,5,9‐Te₃(CH₂)₉, 1,8,15‐Te₃(CH₂)₁₈, 1,7,13,19‐Te₄(CH₂)₂₀, 1,8,15,22‐Te₄(CH₂)₂₄ and 1,9,17,25‐Te₄(CH₂)₂₈ lead to tubular packing of the molecules, as has been observed previously for related thio‐ and selenoether rings. The nature of the intermolecular interactions was explored by solid‐state PBE0‐D3/pob‐TZVP calculations involving periodic boundary conditions. The molecular packing in 1,7,13,19‐Te₄(CH₂)₂₀, 1,8,15,22‐Te₄(CH₂)₂₄ and 1,9,17,25‐Te₄(CH₂)₂₈ forms infinite shafts. The electron densities at bond critical points indicate a narrow range of Te⋅⋅⋅Te bond orders of 0.12–0.14. The formation of the shafts can be rationalized by frontier orbital overlap and charge transfer.