Spectroscopic, electrochemical, and structural properties of 2,6-dialkoxy-9,10-anthraquinones (Anth-OCn, n = 4, 6, 8, 10, and 12) of increasing alkoxy substituents length were investigated. UV–vis spectroscopy showed a substitution-induced bathochromic shift of the least energetic band from 325 nm in the case of unsubstituted anthraquinone to ca. 350 nm for the studied derivatives. Similarly as unsubstituted anthraquinone, the studied compound showed two reversible one electron reductions to a radical anion and spinless anions, respectively. The first reduction was affected by electron-donating properties of the substituents, its potential being shifted to ca. −1.5 V (vs Fc/Fc+), i.e., by 80 to 95 mV as compared to the case of unsubstituted anthraquinone. This corresponded to a decrease of |EA| from 3.27 to 3.19–3.17 eV. The experimental spectroscopic and electrochemical data were in full agreement with the DFT calculations. The introduction of the alkoxy substituent improved solution processibility of the studied compounds and facilitated the formation of their ordered supramolecular 2D aggregation on HOPG as well as single crystal growth from solutions. Comparative structural investigations carried out on single crystals and monolayers deposited on HOPG revealed two, mutually related, effects of the substituent length on the resulting supramolecular organization. The first one concerns both the 2D organization in the monolayers and 3D molecular arrangement in crystals: increasing substituent length evolution of the structure occurs from herringbone-type to lamellar. The second effect, observed in monolayers of the derivatives with longer substituents, concerns gradual evolution of their lamellar structures with increasing substituent length. This evolution is induced by the structure of the graphite substrate and involves increasing correlation of the molecules orientation (anthraquinone cores as well as alkoxy substituents) with the symmetry of the graphite substrate. As a result, their 2D and 3D structures become dissimilar.

The approach to a series of six‐ and seven‐membered oxaboraheterocycles based on naphthalene or biphenyl backbones was developed. The key synthetic step involved Br/Li exchange in respective potassium (bromoaryl)trifluoroborates followed by quenching with selected electrophiles (CO2, DMF, Me2Si(H)Cl) and hydrolytic workup. Two ring‐expanded benzoxaborole congeners were obtained by an additional reduction step with LiAlH4 or NaBH4. The obtained boracyclic compounds were characterized in detail by NMR spectroscopy and single‐crystal X‐ray diffraction. Specifically, biphenyl‐based systems show dynamic behaviour interpreted in terms of inversion of non‐planar seven‐membered boraheterocycles. The acidity of the obtained compounds varies very strongly (pKa ranges from 3.1–9.6) depending on their structure. Due to the enhanced boron Lewis acidity, selected compounds were used as a basis for luminescent complexes with 8‐hydroxyquinoline. A strong phase‐dependent variation of emission‐band maximum (480–527 nm) and photoluminescence quantum yield (10–95 %) was observed, which was rationalized in terms of specific aggregation effects.

A series of solvatomorphic structures of tetrakis(4-dihydroxyborylphenyl)adamantane were investigated.

Five D-π-A-π-D compounds consisting of the same donor unit (dithieno[3,2- b :2′,3′- d ]pyrrole, DTP ), the same π-linker (2,5-thienylene), and different acceptors of increasing electron-withdrawing ability (1,3,4-thiadiazole ( TD ), benzo[ c ][1,2,5]thiadiazole ( BTD ), 2,5-dihydropyrrolo[3,4- c ]pyrrole-1,4-dione ( DPP ), 1,2,4,5-tetrazine ( TZ ), and benzo[ lmn ][3,8]phenanthroline-1,3,6,8(2 H ,7 H )-tetraone ( NDI )) were synthesized. DTP-TD , DTP-BTD , and DTP-DPP turned out to be interesting luminophores emitting either yellow ( DTP-TD) or near-infrared ( DTP-BTD and DTP-DPP ) radiation in dichloromethane solutions. The emission bands were increasingly bathochromically shifted with increasing solvent polarity. Electrochemically determined electron affinities (|EA|s) were found to be strongly dependent on the nature of the acceptor changing from 2.86 to 3.84 eV for DTP-TD and DTP-NDI , respectively, while the ionization potential (IP) values varied only weakly. Experimental findings were strongly supported by theoretical calculations, which correctly predicted the observed solvent dependence of the emission spectra. Similarly, the calculated IP and EA values were in excellent agreement with the experiment. DTP-TD , DTP-BTD , DTP-TZ , and DTP-NDI could be electropolymerized to yield polymers of very narrow electrochemical band gap and characterized by redox states differing in color coordinates and lightness. Poly(DTP-NDI) and poly(DTP-TD) showed promising electrochromic behavior, not only providing a rich color palette in the visible but also exhibiting near-infrared (NIR) electrochromism.