A series of molecular dyads has been synthesized and fully characterised. These linear, donor–spacer–acceptor compounds comprise terminal dyes selected to exhibit intramolecular electronic energy transfer (EET) along the molecular axis. The spacer is built by accretion of ethynylene–carborane units that give centre-to-centre separation distances of 38, 57, 76, 96, and 115 Å respectively along the series. The probability of one-way EET between terminals depends on the length of the spacer but also on temperature and applied pressure. Throughout the series, the derived EET parameters are well explained in terms of through-space interactions but the probability of EET is higher than predicted for the fully extended conformation except in a glassy matrix at low temperature. The implication is that these spacers contract under ambient conditions, with the extent of longitudinal contraction increasing under pressure but decreasing as the temperature is lowered. Longer bridges are more susceptible to such distortion, which is considered to resemble a concertina effect caused by out-of-plane bending of individual subunits. The dynamics of EET can be used to estimate the strain energy associated with molecular contraction, the amount of work done in effecting the structural change and the Young's modulus for the bridge.
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