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Energy Transfer in Near-Orthogonally Arranged Chromophores Separated through a Single Bond

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posted on 14.06.2012, 00:00 by Rijo T. Cheriya, Jimmy Joy, Andrews P. Alex, Anil Shaji, Mahesh Hariharan
A combined experimental and theoretical study shows a significant barrier (ca. 100 kJ/mol) to rotation through the interchromophoric carbon–carbon single covalent (1.49 Å) bond between the naphthalenimide and perylenimide units that prevents coplanarization of the two units in the dyad NP, thereby forcing them to act as independent chromophores/redox centers. Upon photoexcitation, highly efficient energy transfer is observed from the naphthalenimide (energy donor) to the perylenimide (energy acceptor) moiety predominantly through Coulombic coupling, completely isolating the orbital overlap (Dexter-type) interaction between the chromophoric units at such short separation by virtue of their orthogonal arrangement. Because Förster’s ideal-dipole approximation ignores the contribution from significant higher-order Coulombic interactions at such short distances between donor and acceptor moieties, the complete coupling was computed from the transition densities, giving an estimate of the energy-transfer rate from the naphthalenimide donor to the perylenimide acceptor of kET = 2.2 × 1010 s–1, in agreement with observations. Ultrafast excitation energy (ca. 40 ps, 90%) and electron (<0.5 ps, 10%) transfer from the singlet excited state of naphthalenimide to the perylenimide moiety competes with further delayed processes in the conjugate NP. Upon excitation at 345 nm, conjugate NP exhibits near-quantitative energy transfer in conjunction with solvent-polarity-dependent (solvatochromic) perylenimide fluorescence, resulting in a remarkable Stoke’s shift of ca. 175–240 nm. Favorable photophysical properties such as high fluorescence quantum yield, wide excitation range, ultrafast energy transfer, marginal electron transfer, and large Stoke’s shift make this conjugate a potential candidate for biological applications.