Ground-State Electronic Structure in Charge-Transfer Complexes Based on Carbazole and Diarylamine Donors

Abstract

The geometries, binding energies, and amounts of charge transferred in the ground state for a series of donor/acceptor organic π–π complexes have been characterized at the density functional theory level. We find that these compounds exhibit important changes in geometry upon complexation that is accompanied by a large binding energy. The amount of charge transferred from the donor to the acceptor depends highly on the substitution of the donor and can be roughly described by the electron donating or withdrawing ability of the substituent. Interestingly, there is a significant difference in the behavior of carbazoles and diarylamines upon substitution.

Auswirkungen von Unebenheiten bei trockenen Druckverbindungen von Betonbauteilen

“…We note that, in both cases, the cyano groups in the F 4 TCNQ molecule are slightly twisted out of the ring plane. A detailed study of these different motifs has been reported recently 30. Interestingly, in Configuration I, the adsorption energy of F 4 TCNQ on the PA‐modified ITO surface is found to be 0.98 eV; this value is 0.47 eV higher than the binding energy (0.51 eV) for the isolated complex in the absence of the ITO surface, which points to the impact of the presence of the polarizable conducting oxide surface.…”

Surface Modification of Indium‐Tin‐Oxide Via Self‐Assembly of a Donor‐Acceptor Complex: A Density Functional Theory Study

“…A detailed study of these different motifs has been reported recently. [30] Interestingly, in Configuration I, the adsorption energy of F 4 TCNQ on the PA-modified ITO surface is found to be 0.98 eV; this value is 0.47 eV higher than the binding energy (0.51 eV) for the isolated complex in the absence of the ITO surface, which points to the impact of the presence of the polarizable conducting oxide surface.…”

Charge Transfer Complexes of 1,3,6-Trinitro-9,10-phenanthrenequinone with Polycyclic Aromatic Compounds

“…The main structural features of NO 2 groups in I (Table 2), II [11], and III [12] differ only slightly and are close to the average values [16]: the N-O bond lengths in I are in the range from 1.2198(13) to 1.2289(13) Å and the O-N-O valence angles are from 123.79 (10) • to 125.46 (10) • . The nitro groups in structure I at atoms C2, C4, and C9 are rotated out of the aromatic plane by 16.84 (13), 62.75(13) and 13.56(12) • , respectively, which significantly distinguishes them from similar values at atoms C1, C3, and C8 in II (69.02 (19), 0.25 (18), and 19.93(18) • ) [11] and III (73.8(2), 1.35 (15), and 0.95(15) • ) [12]. Unlike structures II and III, where the greatest rotation angle was observed in the NO 2 group at the C 1 atom, experiencing significant steric repulsion from atoms C 10 and H 10 , in structure I steric difficulties arise between the nitro group at the atom C 4 and the carbonyl group O 5 -C 5 , which causes a ~63 • rotation of the NO 2 group and a significant non-planarity of the carbonyl.…”

“…The formation of charge transfer complexes is controlled by the energy difference (∆E MO ) between the LUMO of the isolated acceptor ( A E LUMO ) and the HOMO of the isolated donor ( D E HOMO ) [3,13]. Since A E LUMO is constant for all the considered CTCs and is equal to −4.57 eV, ∆E MO depends only on D E HOMO which varies from −6.97 to −4.37 eV for selected donors.…”