The intervalence (IV) states of the monocationic states of the star-shaped nonaamine (3) and the triamine (2) as the branched unit in 3 have been examined by electrochemical, spectroelectrochemical, and temperature-dependent ESR spectroscopy. The oligoarylamines 2 and 3 were synthesized by using the successive palladium-catalyzed amination reaction. The redox property of 3 was basically the same as that of 2. However, there exist small potential differences between the first three one-electron oxidations for 3, indicating electronic coupling among the peripherally substituted triamine moieties via the central 1,3,5-benzenetriyl bridging unit. The observed ESR spectral pattern for 2+ remained unchanged over the measured temperature range. From the spectral simulation analyses, it was concluded that the unpaired electron in 2+ is fully delocalized over the whole molecule on the ESR time scale. This conclusion was corroborated by comparison of its optical absorption spectrum with TD-DFT-calculated results. In contrast, the peak-to-peak ESR line width (DeltaHPP) of 3+ exhibited temperature dependency. This behavior is ascribed to the thermally activated intramolecular charge transfer (ICT) among the branched three triamine moieties via the central 1,3,5-benzenetriyl bridging unit. From the spectral simulations based on the stochastic Liouville method, the first-order rate constant at each temperature and the parameters of the energy barrier for the ICT in 3+ were successfully determined.

Syntheses of both the dimer (3) and the trimer (4) of all-para-brominated poly(N-phenyl-m-aniline)s (2c) were achieved in a one-pot procedure from the parent nonbrominated oligomers and benzyltrimethylammonium tribromide [(BTMA)Br(3)]. An X-ray crystallographic analysis revealed that 4 has a U-shaped structure, suggesting that 2c easily adopts helical structures. Furthermore, the redox properties were investigated by the UV-vis and EPR measurements. It was confirmed that the both 3 and 4 can be oxidized into the dications 3(2+) and 4(2+) with triplet spin-multiplicity.

Dianisylamino donor (D) and dimesitylboryl acceptor (A) substituents were introduced at the 1,6- and 2,7-positions of pyrene to demonstrate that the substitution patterns influence the photophysical properties. The different pictures in orbital interactions between the pyrene core and the D-A substituents led to the outcome that 1,6-substituted pyrene derivative 1 had stronger electron-donating and electron-accepting properties in conjunction with a small HOMO-LUMO gap, as compared to the 2,7-substituted derivative. For these pyrene derivatives, modest (Φ = 0.2) to strong (Φ = 1.0) fluorescence was detected in degassed organic solvents; 1 exhibited a typical intramolecular charge transfer (ICT) emission obeying energy-gap law, while 2 displayed a moderate inverse energy-gap law, originating from the different substitution patterns. Although theoretical calculations predicted that both 1 and 2 adopt highly twisted ICT excited states (TICT excited states) even in the gas phase, but practically, it was suggested that the observed photophysical properties could be determined by the extent of twist angle of the TICT-like excited state in accordance with the solvent polarity. Moreover, the bulky D-A substituents inhibit the intermolecular direct π-π interactions, thereby resulting in the bright and moderate solid-state emissions for 1 (Φ = 0.76) and 2 (Φ = 0.21), respectively.