C_s-Symmetric, Peripherally Fluorinated Boron Subphthalocyanine–Subnaphthalocyanine Hybrids: Shedding New Light on Their Fundamental Photophysical Properties and Their Functionality as Optoelectronic Materials

Hybridization of boron subphthalocyanine (BsubPc) and boron subnaphthalocyanine (BsubNc) has been modestly explored in the past, and was therefore carried out herein to access a subclass of these chromophores denoted as R_a-F_xBsub(Pc_3–p-Nc_p) hybrids, where R_a is the axial halide substituent (axial chloride, Cl-, or axial fluoride, F-), x = 8, and p = 1. These chromophores were targeted as new candidate materials for organic electronic applications due to their C_s symmetry, in-plane dipole moment, and unique photophysical properties. Cl-/F- F₈Bsub(Pc₂-Nc₁) hybrids were compared to Cl-/F- F₈BsubPc hybrids, which are analogous compounds with an identical number of peripheral fluorine atoms but lower degree of π-conjugation. Upon photoexcitation of dilute toluene solutions and doped thin films with polystyrene as a nonemissive host, F₈Bsub(Pc₂-Nc₁) hybrids exhibited distinctively broad absorption spectra and narrow emission profiles with red-shifted peak photoluminescence wavelengths in the 618–623 nm region compared to F₈BsubPc hybrids (581–584 nm). Electroluminescence properties were probed in simple solution-cast organic light-emitting diodes (OLEDs) in which all four hybrids were diluted within an F8BT emissive polymer host. Upon electronic excitation, electroluminescence (EL) of C_s-symmetric hybrids followed the same trends as photoluminescence (PL), with OLED devices displaying narrow EL in the orange region (588–592 nm) for F₈BsubPc hybrids and in the near-red region for F₈Bsub(Pc₂-Nc₁) hybrids (627–632 nm). The photophysical processes important to OLEDs moderately improved with less π-conjugation in the periphery of the C_s-symmetric hybrids [F₈Bsub(Pc₂-Nc₁) vs F₈BsubPc; EQE_Max: 0.099% vs 0.129%; luminance: 500 cd/m²vs 1000 cd/m² at maximum current density; relative PL quantum yields (QYs) ≈ 17–22% vs ≈ 35–44%]. Electrochemical data showed that C_s symmetry introduces reversibility or quasi-reversibility in the oxidation regime at potentials >1 V, and peripheral fluorination enables reversibility in the reduction process. Overall, F₈Bsub(Pc₂-Nc₁) hybrids embody several unique physical characteristics into one: broad absorption spectra (full width at half-maximum height, FWHM_sol^abs = 53–55 nm, FWHM_film^abs = 71 nm), narrow near-red electroluminescence (FWHM_OLED^EL = 33 nm), and photoluminescence (FWHM_sol^PL = 25–26 nm, FWHM_film^PL = 32 nm) emission, small energy band gaps (1.95–1.96 eV), high extinction coefficients (ε ≈ (5.65–6.16) × 10⁴ M^–1 cm^–1), and dual electrochemical versatility. These results provide new physical insights into the material properties of C_s-symmetric macrocycles and advance the consideration of F₈Bsub(Pc₂-Nc₁) and F₈BsubPc hybrids for optoelectronic applications.