E. Fabiano,† F. Della Sala,*,† G. Barbarella,‡ S. Lattante,†,§ M. Anni,†,‖ G. Sotgiu,‡ C. Hättig,⊥ R. Cingolani,† and G. Gigli†,‖

J. Phys. Chem. B 110, 18651-18660 (2006).
Received: May 11, 2006; In Final Form: July 20, 2006

We report a joint theoretical-experimental study on the optical properties of 5-N-succinimidyl-2,2'-bithiophene (NS-2T), a prototype system for a new class of biomarkers. Time-dependent density functional theory (TDDFT) and approximate coupled-cluster single and doubles (CC2) calculations are performed in the ground and excited states. Theoretical results are compared with absorption, photoluminescence (PL), time-resolved PL, and PL quantum efficiency measurements. The excited state of NS-2T has a larger dipole moment as compared to that of the ground state, explaining the experimental shift of the PL peak in solvents of different polarity, and a smaller intersystem crossing (ISC) rate as compared to that of isolated bithiophene (2T), explaining the increased PL quantum efficiency. We also studied two model systems to describe the effects of the covalent binding of NS-2T to biomolecules and proteins with the ε-NH₂ lysine groups. These model systems show optical properties closer to 2T, as the PL quantum efficiency is reduced due to the increased ISC rate. Theoretical calculations and experimental results show that covalent binding of NS-2T to a biomolecule will blue-shift the absorption but not the photoluminescence. CC2 and TD-DFT can very well describe the absorption and photoluminescence energies of all three systems, but the presence of several charge-transfer transitions in the TD-DFT spectrum of NS-2T required the use of a correlated method to validate the TD-DFT results.

^* Author to whom correspondence should be addressed. E-mail:fabio.dellasala@unile.it
^† National Nanotechnology Laboratory of INFM-CNR, Università degli Studi di Lecce.
^‡ ISOF, Area della Ricerca CNR.
^§ Dipartimento di Fisica, Università degli Studi di Lecce.
^‖ Dipartimento di Ingegneria Dell'Innovazione, Università degli Studi di Lecce.
^⊥ Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum.

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