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Four donor-acceptor-donor compounds consisting of 9,9-dimethyl-9,10-dihydroacridine donors differently linked to a benzothiadiazole acceptor were designed using DFT calculations and synthesized, namely 4,7-bis(4-(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[ c ][1,2,5]thiadiazole (1), 4,7-bis(2,5-dimethyl-4-(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[ c ][1,2,5]thiadiazole (2), 4,7-bis(3,5-di(9,9-dimethyl-9,10-dihydroacridine)phenyl)benzo[ c ][1,2,5]thiadiazole (3), and 4-(3,5-di(9,9-dimethyl-9,10-dihydroacridine)phenyl)-7-(thiophen-2-yl)benzo[ c ][1,2,5]thiadiazole (4). As predicted theoretically, all studied compounds were electrochemically active both in the reduction as well as in the oxidation modes. They underwent one electron quasi -reversible reduction. Oxidation of 1 and 2 involved a two electron process transforming them into dications and carrying out, in parallel, their dimerization. Oxidation of 3 and 4 resulted in their oligomerization (polymerization). The electrochemically determined ionisation potentials (IP) of 1-4 were similar, covering a narrow range of 5.28-5.33 eV and were consistent with DFT calculations. Larger differences were found for experimentally determined electron affinity (EA) values, being significantly lower for 2 (|EA| = 2.59 eV) as compared to 1, 3 and 4 whose |EA| values were higher by 0.15-0.25 eV, again consistent with DFT calculations. DFT calculations predict positive values of Δ E (S 1 -T 1 ) for all compounds i.e. in the range of 0.18 eV to 0.43 eV for 1, 3 and 4 and a significantly lower value for 2 (0.06 eV), indicating a possible RISC process in this case. DFT calculations of Δ E (S 1 -T 2 ) lead to negative and very small values for 2-4 implying a possible involvement of higher lying triplets in the generation of singlet excitons. The investigated derivatives exhibited fluorescence in the orange-red spectral range (550-770 nm) and were strongly dependent on the solvent polarity. The highest PLQY value of 37% was measured for 1 in toluene. The PLQY values significantly improved upon deoxygenation of the studied solutions. Solid state samples also exhibited higher PLQY values as compared to those determined for DCM solutions. These findings were rationalized by partial suppression of the vibrationally induced emission quenching in the solid state due to the intermolecular interaction confinement.

Three new donor-acceptor (D-A) compounds, positional isomers of phenoxazine-substituted acridone, namely 1-phenoxazine-N-hexylacridone (o-A), 2-phenoxazine-N-hexylacridone (m-A) and 3-phenoxazine-N-hexylacridone (p-A), were synthesized. The synthesized compounds showed interesting, isomerism-dependent electrochemistry. Their oxidation was reversible and their potential (given vs. Fc/Fc+) changed from 0.21 V for o-A to 0.36 V for p-A. In contrast, their reduction was irreversible, isomerism-independent and occurred at rather low potentials (ca. -2.25 to -2.28 V). The electrochemical results led to the following values of the ionization potentials (IPs) and electron affinities (EAs): 5.03 eV and -2.14 eV, 5.15 eV and -2.20 eV, and 5.20 eV and -2.28 eV for o-A, m-A and p-A, respectively. The experimentally obtained values were in very good agreement with those predicted by DFT calculations. All three isomers readily formed single crystals suitable for their structure determination. o-A and p-A crystallized in P1[combining macron] and P21/n space groups, respectively, with one molecule per asymmetric unit, while m-A crystallized in the P21/c space group with two molecules in the asymmetric unit accompanied by disordered solvent molecules. The UV-vis spectra of the studied compounds were isomerism and solvent independent, yielding absorption maxima in the vicinity of 400 nm. Their photoluminescence spectra, in turn, strongly depended on isomerism and the used solvent showing smaller Stokes shifts for the emission bands registered in toluene as compared to the corresponding bands measured in dichloromethane. The photoluminescence quantum yields (φ) were systematically higher for toluene solutions reaching the highest value of 20% for p-A. For all three isomers studied, stationary and time-resolved spectroscopic investigations carried out in toluene at different temperatures revealed spectral features indicating a contribution of thermally activated delayed fluorescence (TADF) to the observed spectroscopic behaviour. The measured photoluminescence quantum yields (φ) were higher for solid state films of pure compounds and for their dispersions in solid matrices (zeonex) than those recorded for toluene and dichloromethane solutions of the studied phenoxazine-N-hexylacridone isomers. The obtained experimental spectroscopic and structural data were confronted with theoretical predictions based on DFT calculations.

Magnetic properties of a doped linear polyarylamine (PA2), whose chain includes alternating para-phenylene and meta-phenylene groups, and of two cyclic and linear model compounds (C2 and D2) were explored by pulsed-EPR nutation spectroscopy, SQUID magnetometry and DFT calculations. Stoichiometrically doped PA2 samples exhibit a pure S = 1 state (exchange coupling constant J = 18 K) with a high spin concentration (0.65) corresponding to 65% of mers bearing holes. Such properties were already observed for doped reticulated polyarylamines but are quite unusual for doped linear polyarylamines. In order to better understand the properties of PA2, model compounds C2 and D2 were also investigated: pure S = 1 spin states could also be obtained, but with higher J (respectively 57 K and 35 K) and, surprisingly, with high but still limited spin concentrations (respectively 0.77 and 0.65).

Teraaza- and hexaazacyclophanes have been synthesized via a one-step palladium catalyzed amination reaction. The chemical oxidation of cyclophanes leads to the formation of radical cations, the presence of which was manifested by the appearance of new bands in UV-Vis-NIR and IR spectra. Spins of radical cations can be magnetically coupled. The nutation pulsed-EPR technique (PEANUT experiment) enables us to determine the multiplicity of the systems for different oxidant/cyclophane ratios. Spins of cyclophanes oxidized to diradical dications interact ferromagnetically to form a pure triplet state.