Accelerating charge transfer in a triphenylamine–subphthalocyanine donor–acceptor system

Abstract

We have designed, synthesized and probed a dodecafluoro-subphthalocyaninato boron(III) unit, which bears a triphenylamine moiety in its axial position, as a novel electron donor-acceptor system.

Supramolecular Tetrad of Subphthalocyanine–Triphenylamine–Zinc Porphyrin Coordinated to Fullerene as an “Antenna‐Reaction‐Center” Mimic: Formation of a Long‐Lived Charge‐Separated State in Nonpolar Solvent

“…Metal-free asymmetrical porphyrin 6 was prepared according to a typical method for porphyrin synthesis [24] in a yield of 8 %, and subsequent demethylation of the methoxy group in 6 was performed by using BBr 3 to give porphyrin 7 in 69 % yield. The hydroxy group in 7 replaced the axial chlorine atom of SubPc-Cl, which was synthesized according to the literature procedures, [13,14] to produce SubPc-TPA-H 2 P 8 in 10 % yield. Finally, metalation was carried out using zinc acetate to afford SubPc-TPAZnP 1 in 82 % yield.…”

“…The SubPc entity possesses i) strong absorption in the visible region (l = 500-700 nm), ii) higher energy of the singlet excited state (2.16 eV) and triplet excited state (1.40 eV) compared with those of phthalocyanines, and iii) relatively low reorganization energies. [13,14] The covalently linked subphthalocyanine-triphenylamine-zinc porphyrin 1, owing to the presence of three chromophores absorbing different portions of the visible spectrum, guarantees an increased absorption cross-section and an efficient use of the solar energy. Finally, fullerene, [18] the ultimate electron acceptor, [8][9][10][11][12][13][14][15] has been utilized to construct the supramolecular tetrad 2 by a self-assembly approach involving axial coordination.…”

Comparative electronic structures and UV–vis spectra of tribenzosubporphyrin, tribenzomonoazasubporphyrin, tribenzodiazasubporphyrin, and subphthalocyanine: Insight from DFT and TDDFT calculations

“…Subphthalocyanines have nonplanar, bowl-like structures along with a 14 -electron aromatic core with a trigonal-pyramidal boron atom as the central atom. They exhibit strong UV-vis absorption, intense fluorescence, and remarkable nonlinear optical properties and hence can be potentially applied as chromophores in molecular electronics [14][15][16][17][18], nonlinear optics materials [5,[10][11][12][13][19][20][21][22], photodynamic therapy [23,24], and light-harvesting [25][26][27][28][29]. In 2006, the analogues of subphthalocyanines in which all meso-nitrogen atoms were substituted with the sp 2 -hybrid carbons, the tribenzosubporphyrines [30], were synthesized and characterized as their boron complexes.…”

Trifluoroethoxy‐Coating Improves the Axial Ligand Substitution of Subphthalocyanine

“…Their 14 p-electron core also facilitates strong absorption and leads to high emission quantum yields in the visible region. These features make SubPcs promising chromophores with potential applications in optical data storage, [3] nonlinear optics, [4] photosynthetic models for studying energy-and electron-transfer processes, [5] supramolecular chemistry, [6] and photodynamic therapy (PDT). [7] The optoelectronic properties of SubPcs can be fine-tuned by 1) varying their axial ligands and/or 2) peripheral functionalisation.…”