Abstract: | Carbon tetrabromide and bromoform are employed as prototypical electron acceptors to demonstrate the charge‐transfer nature of various intermolecular complexes with three different structural types of electron donors represented by (1) halide and pseudohalide anions, (2) aromatic (π‐bonding) hydrocarbons, and (3) aromatics with (n‐bonding) oxygen or nitrogen centers. UV–Vis spectroscopy identifies the electronic transition inherent to such 1:1] complexes; and their Mulliken correlation with the donor/acceptor strength verifies the relevant charge‐transfer character. X‐ray crystallography of CBr4/HCBr3 complexes with different types of donors establishes the principal structural features of halogen bonding. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:449–459, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20264 |