Abstract : The present works report the first structure–prop-erty relationship study of a key class of organic semiconductors , that is, the four spirobifluorene positional isomers possessing a para-, meta-or ortho-linkage. The remarkable and surprising impact of the ring bridging and of the linkages on the electronic properties of the regioisomers has been particularly highlighted and rationalised. The impact of the ring bridging on the photophysical properties has been stressed with notably the different influence of the linkages and the bridge on the singlet and triplet excited states. The first member of a new family of spirobifluorenes substituted in the 1-position, which presents better performance in blue phosphorescent OLEDs than those of its regioisomers, is reported. These features highlight not only the great potential of 1-substituted spirobifluorenes, but also the remarkable impact of regioisomerism on electronic properties.
