Exothermic intramolecular triplet energy transfer (TET) rate constants:in Various flexible bichromophoric systems D-(CH2)(n)-O-A (D = benzoyl, 4-methylbenzoyl; A = 2-naphthyl, 4-, 3-, 2-biphenyl; n = 3-14) have been determined from steady-state quenching and quantum yield measurements. The magnitude of the rate constants in molecules where n = 3 is comparable to those in molecules with a rigid spacer between chromophores, so that a through-bond mechanism is presumed to remain important. A very gradual drop in TET rate constants as the connecting polymethylene chain becomes longer indicates that through-space interactions compete and apparently provide the only mechanism responsible for transfer when n greater than or equal to 5. Rate constants in long molecules (n = 11-14) remain remarkably high (similar to 10(8) s(-1))-lower than in those with four-atom tethers by only 1 order of magnitude. This effect is explained on the basis of rapid conformational equilibria always keeping a sufficient fraction of the molecules coiled so that the two chromophores are close enough to interact within 10 ns, the time required for the competing gamma-hydrogen abstraction used to monitor triplet lifetimes. Energy transfer accounts for 40-75% of triplet decay for the longer molecules. This high efficiency indicates that only a small fraction involves static quenching in ground-state conformers with the two ends within 4 Angstrom. The majority must represent a combination of rate-determining bond rotations to such geometries and equilibrated conformations with their ends farther apart but still able to undergo energy transfer within 10 ns. Thus, the measured rate constants are, in fact, a weighted average of three different conformational mechanisms. The decrease in rate constant with tether length is not monotonic:: a relative increase in rate for medium-chain-length molecules is explained by a larger number of favorable conformers and further, in biphenyl derivatives, by a rotation along the terminal O-C bond between the tether and the aromatic ring. As was expected, replacement of the polymethylene tether with poly(ethylene oxide) promotes better flexibility and thus higher transfer rates. Rate constants were found to be lower by a factor of similar to 2 when biphenyl rather than naphthyl is the acceptor, in agreement with earlier bimolecular measurements. With the 4-methylbenzoyl group (pi,pi* lowest triplet) as donor instead of benzoyl (n,pi* lowest triplet), a small (similar to 1.5x) but consistent rate increase occurred for all tether lengths.