The second-order nonlinear optical (NLO) properties of two tetrathiafulvalene (TTF)-fused electron donor-acceptor dyads have been determined using the Electric Field Induced Second Harmonic generation (EFISH) technique and theoretically rationalized. Dyads TTF-dppz (1) and TTF-BTD (2) were obtained by direct fusion of a TTF electron donor unit either with a dipyrido[3,2-a:2′,3′-c]phenazine (dppz) or a benzothiadiazole (BTD) electron acceptor moiety. Dyad 1 acts as a reversible acido-triggered NLO switch by protonation/deprotonation at two nitrogen atoms of the dppz acceptor moiety induced by sequential exposure to HCl and ammonia vapors. Dyad 2, on the other hand, displays redox-tunable NLO properties upon two consecutive oxidations to its radical cation 2+and dication 22+species. The resulting final dication 22+exhibits an inversion of the sign of β0, due to a completely inverted distribution of the frontier molecular orbitals with respect to those of its neutral species, leading to a scarcely polar species in the excited state, as indicated by the theoretical calculations.
Stimuli-responsive NLO properties of tetrathiafulvalene-fused donor-acceptor chromophores / E. Cariati, X. Liu, Y. Geng, A. Forni, E. Lucenti, S. Righetto, S. Decurtins, S.-. Liu. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - 19:33(2017), pp. 22573-22579. [10.1039/c7cp04687a]
Stimuli-responsive NLO properties of tetrathiafulvalene-fused donor-acceptor chromophores
E. Cariati;S. Righetto;
2017
Abstract
The second-order nonlinear optical (NLO) properties of two tetrathiafulvalene (TTF)-fused electron donor-acceptor dyads have been determined using the Electric Field Induced Second Harmonic generation (EFISH) technique and theoretically rationalized. Dyads TTF-dppz (1) and TTF-BTD (2) were obtained by direct fusion of a TTF electron donor unit either with a dipyrido[3,2-a:2′,3′-c]phenazine (dppz) or a benzothiadiazole (BTD) electron acceptor moiety. Dyad 1 acts as a reversible acido-triggered NLO switch by protonation/deprotonation at two nitrogen atoms of the dppz acceptor moiety induced by sequential exposure to HCl and ammonia vapors. Dyad 2, on the other hand, displays redox-tunable NLO properties upon two consecutive oxidations to its radical cation 2+and dication 22+species. The resulting final dication 22+exhibits an inversion of the sign of β0, due to a completely inverted distribution of the frontier molecular orbitals with respect to those of its neutral species, leading to a scarcely polar species in the excited state, as indicated by the theoretical calculations.File | Dimensione | Formato | |
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