Near-Infrared Absorbing Aza-BODIPY Dyes for Optoelectronic Applications.

Organic dyes that absorb light in the visible to near-infrared region have garnered significant interest, owing to their extensive utility in organic photovoltaics and various biomedical applications. Aza-boron-dipyrromethene (Aza-BODIPY) dyes are a class of chromophores with impressive photophysical properties such as tunable absorption from the visible region towards near infrared (NIR) region, high molar absorptivity, and fluorescence quantum yield. In this review, we discuss the developments in the aza-BODIPYs, related to their synthetic routes, photophysical properties and their applications. Their design strategies, modifications in chemical structures, mode/position of attachment, and their impact on photo-physical properties are reviewed. The potential applications of aza-BODIPY derivatives such as organic solar cells, photodynamic therapy, boron-neutron capture therapy, fluorescence sensors, photo-redox catalysis, photoacoustic probes and optoelectronic devices are explained.

Near-IR-Absorbing Bis-Donor Functionalized Aza-BODIPY Derivatives: Synthesis and Photophysical Study by Using Transient Optical Spectroscopy.

A series of near-IR absorbing 2,6-diarylated BF2-chelated aza-boron-dipyrromethenes (aza-BDPs) derivatives bearing different electron donors (benzene, naphthalene, phenanthrene, phenothiazine and carbazole) were designed and synthesized. The effect of different electron donor substitutions on the photophysical properties was studied by steady-state UV-vis absorption and fluorescence spectra, electrochemical, time-resolved nanosecond transient absorption (ns-TA) spectroscopy and theoretical computations. The UV-vis absorption spectra of AzaBDP-PTZ and AzaBDP-CAR (λabs=710 nm in toluene) showed a bathochromic absorption profile compared with the reference AzaBDP-Ph (λabs=685 nm in toluene), indicating the non-negligible electronic interaction at the ground state between donor and acceptor moieties. Moreover, the fluorescence is almost completely quenched for AzaBDP-PTZ/AzaBDP-CAR (fluorescence quantum yield, ΦF=0.2-0.7 % in toluene) as compared with the AzaBDP-Ph (ΦF=27 % in toluene). However, the apparent intersystem crossing ability of these compounds is poor, based on the singlet oxygen quantum yield (ΦΔ=0.3-1.5 %). The ns-TA spectral study showed typical Bodipy localized triplet state transient features, short-lived excited triplet state for AzaBDP-Ph (τT=53.2 µs) versus significantly long-lived triplet state for AzaBDP-CAR (τT=114 µs) was observed under deaerated experimental conditions. These triplet state lifetimes are much longer than that obtained with diiodoAzaBDP (intramolecular heavy atom effect, τT=1.5~7.2 µs). These information are useful for molecular structure design of triplet photosensitizers, for which longer triplet state lifetimes are usually desired. Theoretical computations displayed that the triplet state is mainly localized on the AzaBDP core, moreover, it was found that the HOMO/LUMO energy gap decreased after introducing donor moieties to the skeleton as compared with the reference.

Zinc Tetrapyrrole Coordinated to Imidazole Functionalized Tetracyanobutadiene or Cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene Conjugates: Dark vs. Light-Induced Electron Transfer.

Using the popular metal-ligand axial coordination self-assembly approach, donor-acceptor conjugates have been constructed using zinc tetrapyrroles (porphyrin (ZnP), phthalocyanine (ZnPc), and naphthalocyanine (ZnNc)) as electron donors and imidazole functionalized tetracyanobutadiene (Im-TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene (Im-DCNQ) as electron acceptors. The newly formed donor-acceptor conjugates were fully characterized by a suite of physicochemical methods, including absorption and emission, electrochemistry, and computational methods. The measured binding constants for the 1 : 1 complexes were in the order of 104 -105  M-1 in o-dichlorobenzene. Free-energy calculations and the energy level diagrams revealed the high exergonicity for the excited state electron transfer reactions. However, in the case of the ZnNc:Im-DCNQ complex, owing to the facile oxidation of ZnNc and facile reduction of Im-DCNQ, slow electron transfer was witnessed in the dark without the aid of light. Systematic transient pump-probe studies were performed to secure evidence of excited state charge separation and gather their kinetic parameters. The rate of charge separation was as high as 1011  s-1 suggesting efficient processes. These findings show that the present self-assembly approach could be utilized to build donor-acceptor constructs with powerful electron acceptors, TCBD and DCNQ, to witness ground and excited state charge transfer, fundamental events required in energy harvesting, and building optoelectronic devices.

Far-Red Excitation Induced Electron Transfer in Bis Donor-AzaBODIPY Push-Pull Systems; Role of Nitrogenous Donors in Promoting Charge Separation.

A far-red absorbing sensitizer, BF2 -chelated azadipyrromethane (azaBODIPY) has been employed as an electron acceptor to synthesize a series of push-pull systems linked with different nitrogenous electron donors, viz., N,N-dimethylaniline (NND), triphenylamine (TPA), and phenothiazine (PTZ) via an acetylene linker. The structural integrity of the newly synthesized push-pull systems was established by spectroscopic, electrochemical, spectroelectrochemical, and DFT computational methods. Cyclic and differential pulse voltammetry studies revealed different redox states and helped in the estimation of the energies of the charge-separated states. Further, spectroelectrochemical studies performed in a thin-layer optical cell revealed diagnostic peaks of azaBODIPY⋅- in the visible and near-IR regions. Free-energy calculations revealed the charge separation from one of the covalently linked donors to the 1 azaBODIPY* to yield Donor⋅+ -azaBODIPY⋅- to be energetically favorable in a polar solvent, benzonitrile, and the frontier orbitals generated on the optimized structures helped in assessing such a conclusion. Consequently, the steady-state emission studies revealed quenching of the azaBODIPY fluorescence in all of the investigated push-pull systems in benzonitrile and to a lesser extent in mildly polar dichlorobenzene, and nonpolar toluene. The femtosecond pump-probe studies revealed the occurrence of excited charge transfer (CT) in nonpolar toluene while a complete charge separation (CS) for all three push-pull systems in polar benzonitrile. The CT/CS products populated the low-lying 3 azaBODIPY* prior to returning to the ground state. Global target (GloTarAn) analysis of the transient data revealed the lifetime of the final charge-separated states (CSS) to be 195 ps for NND-derived, 50 ps for TPA-derived, and 85 ps for PTZ-derived push-pull systems in benzonitrile.

Interfacing High-Energy Charge-Transfer States to a Near-IR Sensitizer for Efficient Electron Transfer upon Near-IR Irradiation.

Push-pull systems comprising of triphenylamine-tetracyanobutadiene (TPA-TCBD), a high-energy charge-transfer species, are linked to a near-IR sensitizer, azaBODIPY, for promoting excited-state CS. These systems revealed panchromatic absorption owing to intramolecular CT and near-IR absorbing azaBODIPY. Using electrochemical and computational studies, energy levels were established to visualize excited state events. Fs-TA studies were performed to monitor excited state CT events. From target analysis, the effect of solvent polarity, number of linked CT entities, and excitation wavelength dependence in governing the lifetime of CS states was established. Electron exchange between two TPA-TCBD entities in 3 seem to prolong lifetime of the CS state. We have been successful in demonstrating efficient CS upon both high-energy CT and low-energy near-IR excitations, signifying importance of these push-pull systems for optoelectronic applications operating in the wide optical window.