A series of self-organizing bent-core derivatives 1[12,n], containing a highly π-delocalized stable radical as the central angular structural element, is described. The planarity of the open-shell core permits efficient π–π stacking, which results in the formation of B2 and soft crystalline phases above 100 °C. Optical, XRD and dielectric analyses of 1[12,12] indicate that the ground state of the observed B2 phase is polar antiferroelectric of type SmC_AP_A exhibiting tristable electro-optical switching. SQUID and EPR measurements revealed strong antiferromagnetic spin–spin exchange interactions below the isotropic phase, which have been estimated at θ = −46 cm⁻¹ with the Curie–Weiss law. Transient photoconductivity was observed in the B2 phase with a hole carrier mobility μ_h of 1.4 × 10⁻⁴ cm² V⁻¹ s⁻¹.

A series of bent-core mesogens 2[m,n] and 3[4,6][6,n] derived from the 1,4-dihydrobenzo[e][1,2,4]triazin-4-yl radical and containing two partially fluorinated alkyl tails and the non-fluorinated derivative 1[12] were prepared and investigated by optical, thermal, XRD and magnetic methods. All compounds with six CF₂ units in each terminal tail (2[6,n]) exhibit a smectic A phase with clearing temperatures in a range of 150–180 °C. Introduction of two different alkyl chain lengths into the molecular structure of 2 depressed the SmA–I transition temperature to about 120 °C in 3[4,6][6,n]. Solid-state EPR and magnetic susceptibility measurements (SQUID) for 3[4,6][6,8] revealed paramagnetic behaviour with weak intermolecular spin–spin interactions in the SmA phase suggesting low organization of the spin containing molecular units.

Substitution of the parent [closo-B₁₀H₉-1-NC₅H₅]⁻either at the B(10) position or at the pyridine ring tunes absorption and emission energy.

A series of isomeric supermolecular bi-and tri-radicals, in which “half disc” mesogens are connected 1,4- and 1,3,5-through benzene, respectively, are investigated for liquid crystalline (optical, thermal and powder XRD methods) and magnetic properties (SQUID and VT-EPR methods). The results demonstrate diverse phase structures of the bi- and tri-radicals, which self-organize into Col_r, Col_h, and Col_h(3D) phases. Magnetic data revealed intermolecular ferromagnetic interactions in the solid-state only in bi- and tri-radicals with the connection at the C(3) position, for which the Weiss constant θ (7.8 and 5.2 K, respectively; from Curie–Weiss analysis) and J/k_B exchange interaction energy (2.74 and 3.14 K, respectively; from Baker thermal expansion analysis) were obtained. Variable temperature EPR data demonstrated an increase of signal intensity in most liquid crystalline phases and continuous increase above the mesophase-isotropic liquid transition in two biradicals. Overall results indicate that the dumbbell shape (biradicals) and connection through the C(3) position are most favorable for mesogenic and non-trivial magnetic properties in the series.

A convenient synthesis of [ closo -B ₁₀ H ₈ -1,10-(COOH) ₂ ] ²⁻ leads to a new class of stable diaminocarbonium ylides.