A theoretical base for optimising intermolecular interactions driving polarity formation in channel-type host–guest materials

Spontaneous polarity formation in channel-type host–guest materials is analysed by a Markov model of growth. Criteria for the strength of collinear intermolecular interaction energies Eij between acceptor–π–donor (A–π–D) guest molecules are discussed in order to optimise characteristic properties of the system. In the case of bulk growth, the sequence EAA≫EAD≈EDD is producing (i) high values of net polarity nnet, (ii) a low number of attachments q to reach constant values of nnet, and (iii) a low density of orientational defects η within polar chains. Similarly, the optimum sequence for the growth of oriented films on substrates featuring uniform interactions to guest molecules is: EAA>EDD≫EAD.