Abstract: The geometrical twist of aryl-aryl bond in biphenyl by weakly coordinating anion and selone at the para position has not been clear so far. We report here the synthesis and investigation into the diverse structural properties of biphenyl with weakly coordinating biphenyl imidazolium salts and neutral imidazole selone that exhibit three atropisomers of biphenyl. The approaches underline the diversity of the effects of para substituent with dynamic nature at biphenyl molecule. Graphical Abstract: SYNOPSIS The synthesis and investigation into the diverse structural properties of three atropisomers of biphenyl tuned by para substituted weakly coordinating imidazolium salts and neutral imidazole selone are reported. [Figure not available: see fulltext.]. © 2018, Indian Academy of Sciences.