This review presents a discussion of the conformation of biphenyl derivatives in different chemical environments. The interplay between aromatic stabilization and steric repulsion, normally considered to explain the conformation of the molecule, is contrasted with the interpretation provided by models not based on molecular orbitals. The electronic control of conformation by means of appropriate hydrogen substitution is discussed by examples taken from chemistry and molecular electronics. Supramolecular synthons involving biphenyl are critically analyzed in terms of the molecular conformation, crystal packing and intermolecular forces. Some directions of future research in the control of the conformation of biphenyls are also presented.
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