Synthesis, Optical Properties, and Fluorescence Cell Imaging of Novel Mixed Fluorinated Subphthalocyanines

Abstract

Subphthalocyanines (SubPcs) are a kind of tripyrrolic macrocycle with a boron atom at their core. Incorporating different units onto the SubPc periphery can endow them with various unique properties. Herein, a series of novel fluorinated low-symmetry SubPc derivatives containing chlorine groups (F8-Cl4-SubPc, F4-Cl8-SubPc) and methoxy groups (F8-(OCH3)2-SubPc) were synthesized and characterized by spectral methods (MS, FT-IR, 1H, 13C, 11B, and 19F NMR spectroscopy), and the effect of the peripheral substituents on their electronic structure of low-symmetry macrocycle was investigated by cyclic voltammetry, theoretical calculation, electronic absorption, and emission spectroscopy. In contrast to perfluorinated SubPcs, these low-symmetry SubPcs revealed non-degenerate LUMO and LUMO + 1 orbitals, especially F8-(OCH3)2-SubPc, which was consistent with the split Q-band absorptions. The cyclic voltammetry revealed that these SubPcs exhibited two or three reduction waves and one oxidation wave, which is consistent with the reported SubPcs. Finally, an intracellular fluorescence imaging study of these compounds revealed that these compounds could enter cancer cells and be entrapped in the lysosomes, which provides a possibility of future applications in lysosome fluorescence imaging and targeting.

First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative

“…It is noteworthy that unsymmetrical subphthalocyanines bearing perfluorinated and unsubstituted benzene or naphthalene subunits were studied as probes for visualizing fluorescence for MDA-MB-231 or Hela cells. [29,30] Fusion of seven-membered 1,4-diazepine fragments strongly changes the properties of the porphyrazine-type macrocycle [4,[31][32][33][34][35][36] due to their electronic features as quasi-aromatic systems, 6H/1H tautomerism and ability for intermolecular H-bonding [20] or intramolecular charge transfer. [35] Moreover, 1,4-diazepine rings could be an elegant post-functionalization platform for the synthesis of a new hybrids based on porphyrazine-type macrocycles.…”

“…Among low‐symmetry [ s Pc] analogues, macrocycles containing, along with one or two perfluorinated benzene rings, fused naphthalene, [10,23] pyrene, [24] 1,2,5‐thiadiazole or 1,2,5‐selenadiazole [25,26] and pyrazine [27,28] fragments were described. It is noteworthy that unsymmetrical subphthalocyanines bearing perfluorinated and unsubstituted benzene or naphthalene subunits were studied as probes for visualizing fluorescence for MDA‐MB‐231 or Hela cells [29,30] …”