Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT

Abstract

From X-ray structure analysis, amino twist angles of 90.0° for 2,4-dimethyl-3-(dimethylamino)benzonitrile (mMMD), 82.7° for 4-(di-tert-butylamino)benzonitrile (DTABN), and 88.7° for 6-cyanobenzoquinuclidine (CBQ) are determined, all considerably larger than the 57.4° of 3,5-dimethyl-4-(dimethylamino)benzonitrile (MMD). This large twist leads to lengthening of the amino-phenyl bond, 143.5 pm (mMMD), 144.1 pm (DTABN), 144.6 pm (CBQ), and 141.4 pm (MMD), as compared with 136.5 pm for the planar 4-(dimethylamino)benzonitrile (DMABN). As a consequence, the electronic coupling between the amino and phenyl subgroups in mMMD, DTABN, CBQ, and MMD is much weaker than in DMABN, as seen from the strongly reduced molar absorption coefficients. The fluorescence spectrum of MMD in n-hexane at 25 °C consists of two emissions, from a locally excited (LE) and an intramolecular charge transfer (ICT) state, with a fluorescence quantum yield ratio Φ'(ICT)/Φ(LE) of 12.8. In MeCN, a single ICT emission is found. With mMMD in n-hexane, in contrast, only LE fluorescence is observed, whereas the spectrum in MeCN originates from the ICT state. These differences are also seen from the half-widths of the overall fluorescence bands, which in n-hexane are larger for MMD than for mMMD, decreasing with solvent polarity for MMD and increasing for mMMD, reflecting the disappearance of LE and the onset of ICT in the overall spectra, respectively. From solvatochromic measurements the dipole moments μe(ICT) of MMD (16 D) and mMMD (15 D) are obtained. Femtosecond excited state absorption (ESA) spectra at 22 °C, together with the dual (LE + ICT) fluorescence, reveal that MMD in n-hexane undergoes a reversible LE ⇄ ICT reaction, with LE as the precursor, with a forward rate constant ka = 5.6 × 10(12) s(-1) and a back-reaction kd ∼ 0.05 × 10(12) s(-1). With MMD in the strongly polar solvent MeCN, ICT is faster: ka = 10 × 10(12) s(-1). In the case of mMMD in n-hexane, the ESA spectra show that ICT does not take place, contrary to MeCN, in which ka = 2.5 × 10(12) s(-1). The ICT reactions with MMD and mMMD are much faster than that of the parent compound DMABN in MeCN, with ka = 0.24 × 10(12) s(-1). Because of the very short ICT reaction times of 180 fs (MMD, n-hexane), 100 fs (MMD, MeCN), and 400 fs (mMMD, MeCN), it is clear that the picosecond fluorescence decays of these systems appear to be single exponential, due to the insufficient time resolution of 3 ps. It is concluded that the faster LE → ICT reaction of MMD as compared with DMABN (ka = 0.24 × 10(12) s(-1) in MeCN) is caused by a smaller energy gap ΔE(S1,S2) between the lowest singlet excited states and not by the large amino twist angle. Similarly, the larger ΔE(S1,S2) of mMMD as compared with MMD is held responsible for its smaller ICT efficiency (no reaction in n-hexane).

Blue Light Emitting Polyphenylene Dendrimers with Bipolar Charge Transport Moieties

“…They also indicate that the dual emission for D2 in polar solvents is due to the transformation of localized excited state (S1) into the ICT state which is much stabilized in highly polar environments (see Scheme S2). Similar S 1 →ICT conversions were also discovered in some small molecules [47,48]. Whether the ICT state is due to a more twisted or more planarized molecular structure than in the ground state [34,49], is not investigated here.…”

Regio- and conformational isomerization critical to design of efficient thermally-activated delayed fluorescence emitters

“…There is a great deal of previous work on the observation of dual fluorescence in organic systems1819202122. However these have overwhelmingly displayed emission from a locally excited (LE) singlet state and a singlet CT state18192021.…”

“…However these have overwhelmingly displayed emission from a locally excited (LE) singlet state and a singlet CT state18192021. The observation of dual emission arising from two equally stable CT states of a molecule is a more recently discovered phenomenon22, and in the following systems is as a result of the folding of the PTZ donor unit.…”

Direct Observation of Cascade of Photoinduced Ultrafast Intramolecular Charge Transfer Dynamics in Diphenyl Acetylene Derivatives: Via Solvation and Intramolecular Relaxation

“…However the dynamics of the charge transfer processes are significantly controlled by solvation dynamics and intramolecular relaxation [10][11] . A large number of experimental [12][13][14][15][16][17][18][19][20] and theoretical 6,[21][22][23][24][25][26] studies have been devoted to understand the underlying mechanism controlling the electronic pathways, geometrical structure and dynamics of the photoinduced intramolecular charge transfer (ICT) state in the excited state relaxation of the different electron donor-acceptor -conjugated systems upon photoexcitation [4][5] . Though the characteristics of the ICT state with dual fluorescence are described by different models including planar 27 , partially twisted or pre twisted 28 , twisted 29 , rehybridized 30 and multifaceted dynamics 31 , controversies on the mechanism of ICT are prevalent 21,26,[32][33] .…”