Strong Electron Donor Research Articles

Comparative Study of Iminodibenzyl and Diphenylamine Derivatives as Hole Transport Materials in Inverted Perovskite Solar Cells.

Perovskite solar cells (PSCs) have recently achieved over 26% power conversion efficiency, challenging the dominance of silicon-based alternatives. This progress is significantly driven by innovations in hole transport materials (HTMs), which notably influence the efficiency and stability of PSCs. However, conventional organic HTMs like PTAA, although highly efficient, suffer from thermal degradation, moisture ingress, and high cost. This study explores the potential of iminodibenzyl, a moiety known for its strong electron-donating capabilities in pharmaceutical applications, as a novel HTM. A series of fluorene-based derivatives incorporating iminodibenzyl (TMF-2 and TDF-2) and diphenylamine (TMF-1 and TDF-1) units were synthesized and characterized. The new HTMs demonstrated commendable optical, electrochemical, and thermal properties, as well as enhanced photostability. Among them, TDF-2 achieved a power conversion efficiency (PCE) of 19.38%, the highest of the new materials. Although these efficiencies are slightly lower than the benchmark PTAA (20.20%), the study underscores the potential of iminodibenzyl to enhance photostability and increase HOMO levels, making it a promising candidate for future HTM development in PSCs.

A Trithia‐Bridged N‐Heterotriangulene: The Hitherto Missing Electron Donor

AbstractThe very first representative of trithia‐bridged N‐heterotriangulene, a triphenylamine with sulfur atoms bridging the ortho‐positions, was synthesized by a sequence of regioselective sulfenylation with phthalimidesulfenyl chloride followed by Lewis acid‐catalyzed electrophilic cyclization. X‐ray crystallography revealed a saddle‐shaped geometry of the polycyclic scaffold. UV/Vis absorption spectroscopy and cyclic voltammetry were used to characterize the optoelectronic properties. The title compound is a particularly strong electron donor forming a perfectly stable radical cation, which was analyzed by electron paramagnetic resonance spectroscopy and X‐ray crystallography. The electron donor properties were further highlighted by the formation of crystalline donor‐acceptor complexes with strong cyano‐based acceptors.

A Trithia-Bridged N-Heterotriangulene: The Hitherto Missing Electron Donor.

The very first representative of trithia-bridged N-heterotriangulene, a triphenylamine with sulfur atoms bridging the ortho-positions, was synthesized by a sequence of regioselective sulfenylation with phthalimidesulfenyl chloride followed by Lewis acid-catalyzed electrophilic cyclization. X-ray crystallography revealed a saddle-shaped geometry of the polycyclic scaffold. UV/Vis absorption spectroscopy and cyclic voltammetry were used to characterize the optoelectronic properties. The title compound is a particularly strong electron donor forming a perfectly stable radical cation, which was analyzed by electron paramagnetic resonance spectroscopy and X-ray crystallography. The electron donor properties were further highlighted by the formation of crystalline donor-acceptor complexes with strong cyano-based acceptors.

Spatial Conformation Engineering of Aromatic Ketones for Highly Efficient and Stable Perovskite Solar Cells.

Carbonyl-containing materials employed in state-of-the-art hybrid lead halide perovskite solar cells (PSCs) exhibit a strong structure-dependent electron donor effect that predominates in defect passivation. However, the impact of the molecular spatial conformation on the efficacy of carbonyl-containing passivators remains ambiguous, hindering the advancement of molecular design for passivating materials. Herein, we show that altering the spatial torsion angle of aromatic ketones from twisted to planar configurations, as seen in benzophenone (BP, 27.2°), anthrone (AR, 15.3°), and 9-fluorenone (FO, 0°), leads to a notable increment of the electron cloud density around the carbonyl group, thus improving the passivation ability for lead-based defects. Consequently, the PSC performance also relies on the torsion angle of the aromatic ketones, with the coplanar FO-based PSC achieving a highest power conversion efficiency (PCE) of 25.13% and retaining 92% of its initial efficiency after 1000 h of operation at the maximum power point under continuous 1-sun illumination (ISOS-L-1I). Moreover, a perovskite mini-module (14.0 cm2) containing FO exhibits a PCE of 20.19%. Our findings highlight the influence of molecular conformation on the passivation effect of the carbonyl group, offering deeper insight into the design and development of aromatic ketones as passivators for highly efficient and stable PSCs.

Platinum-Catalyzed Regio- and Enantioselective Diboration of Unactivated Alkenes with (pin)B-B(dan).

Asymmetric diboration of terminal alkenes is well established, and subsequent selective functionalization of the less hindered primary boronic ester is commonly achieved. Conversely, selective functionalization of the sterically less accessible secondary boronic ester remains challenging. An alternative way to control chemoselective functionalization of bis(boron) compounds is by engendering different Lewis acidity to the two boryl moieties, since reactivity would then be dictated by Lewis acidity instead of sterics. We report herein the regio- and enantioselective Pt-catalyzed diboration of unactivated alkenes with (pin)B-B(dan). A broad range of terminal and cyclic alkenes undergo diboration to furnish the differentiable 1,2-bis(boron) compounds with high levels of regio- and enantiocontrol, giving access to a wide variety of novel building blocks from a common intermediate. The reaction places the less Lewis acidic B(dan) group at the less hindered position and the resulting 1,2-bisboryl alkanes undergo selective transformations of the B(pin) group located at the more hindered position. The regioselectivity of the diboration has been studied by DFT calculations and is believed to originate from the trans influence, which lowers the activation barrier for formation of the regioisomer that places the weaker electron donor [B(pin) vs B(dan)] opposite the strong electron donor (alkyl group) in the platinum complex.

Engineering π‐Electron Bridge Enables Low‐Potential 2D Redox Polymer Anodes for High‐Voltage Aqueous All‐Organic Batteries

AbstractAqueous all‐organic batteries (AAOBs) have emerged as a hot topic but their development was plagued by limited choices of anode materials, generally facing an intractable trade‐off between low potential and high stability. Here, we propose a novel π‐electron bridge engineering strategy to explore a class of 2D dioxin‐bridged redox covalent organic polymer (RCOP) as trade‐off‐breaking anodes for high‐voltage AAOBs. By establishing a tunable RCOP platform, we perform theoretical study to scrutinize how bridge units between active sites affect the electrode potential and redox activity for the first time. We discover that compared to common pyrazine bridge, the weakened conjugation and strong electron donor character of the proposed dioxin bridge can induce elevated LUMO level and enriched π‐electron populations in active sites, heralding a low electrode potential and enhanced redox activity. Besides, the nonaromaticity‐induced molecular flexibility of dioxin bridge mitigates intermolecular stacking for sufficient active sites exposure. To experimentally corroborate this, a new dioxin‐bridged 2D RCOP (D‐HATN) and its pyrazine‐bridged analogue (P‐HATN) are synthesized for proof‐of‐concept demonstration. D‐HATN displays excellent compatibility with Na+/Zn2+/NH4+/H3O+ and obviously lower redox potentials in various dilute electrolytes compared to P‐HATN and most reported organic anodes, while featuring rapid Grotthuss‐type proton conduction and unprecedented durability in acid – 91.8 % capacity retention after 20000 cycles. Thus, the D‐HATN‐involved all‐organic proton battery delivers an average output voltage of 0.75 V, which can be further elevated to 1.63 V with alkaline‐acidic hybrid electrolyte design, affording markedly‐increased specific energy.

Engineering π-Electron Bridge Enables Low-Potential 2D Redox Polymer Anodes for High-Voltage Aqueous All-Organic Batteries.

Aqueous all-organic batteries (AAOBs) have emerged as a hot topic but their development was plagued by limited choices of anode materials, generally facing an intractable trade-off between low potential and high stability. Here, we propose a novel π-electron bridge engineering strategy to explore a class of 2D dioxin-bridged redox covalent organic polymer (RCOP) as trade-off-breaking anodes for high-voltage AAOBs. By establishing a tunable RCOP platform, we perform theoretical study to scrutinize how bridge units between active sites affect the electrode potential and redox activity for the first time. We discover that compared to common pyrazine bridge, the weakened conjugation and strong electron donor character of the proposed dioxin bridge can induce elevated LUMO level and enriched π-electron populations in active sites, heralding a low electrode potential and enhanced redox activity. Besides, the nonaromaticity-induced molecular flexibility of dioxin bridge mitigates intermolecular stacking for sufficient active sites exposure. To experimentally corroborate this, a new dioxin-bridged 2D RCOP (D-HATN) and its pyrazine-bridged analogue (P-HATN) are synthesized for proof-of-concept demonstration. D-HATN displays excellent compatibility with Na+/Zn2+/NH4 +/H3O+ and obviously lower redox potentials in various dilute electrolytes compared to P-HATN and most reported organic anodes, while featuring rapid Grotthuss-type proton conduction and unprecedented durability in acid - 91.8 % capacity retention after 20000 cycles. Thus, the D-HATN-involved all-organic proton battery delivers an average output voltage of 0.75 V, which can be further elevated to 1.63 V with alkaline-acidic hybrid electrolyte design, affording markedly-increased specific energy.

Platinum‐Catalyzed Regio‐ and Enantioselective Diboration of Unactivated Alkenes with (pin)B−B(dan)

AbstractAsymmetric diboration of terminal alkenes is well established, and subsequent selective functionalization of the less hindered primary boronic ester is commonly achieved. Conversely, selective functionalization of the sterically less accessible secondary boronic ester remains challenging. An alternative way to control chemoselective functionalization of bis(boron) compounds is by engendering different Lewis acidity to the two boryl moieties, since reactivity would then be dictated by Lewis acidity instead of sterics. We report herein the regio‐ and enantioselective Pt‐catalyzed diboration of unactivated alkenes with (pin)B−B(dan). A broad range of terminal and cyclic alkenes undergo diboration to furnish the differentiable 1,2‐bis(boron) compounds with high levels of regio‐ and enantiocontrol, giving access to a wide variety of novel building blocks from a common intermediate. The reaction places the less Lewis acidic B(dan) group at the less hindered position and the resulting 1,2‐bisboryl alkanes undergo selective transformations of the B(pin) group located at the more hindered position. The regioselectivity of the diboration has been studied by DFT calculations and is believed to originate from the trans influence, which lowers the activation barrier for formation of the regioisomer that places the weaker electron donor [B(pin) vs B(dan)] opposite the strong electron donor (alkyl group) in the platinum complex.

Highly and Deep Red-Luminescent Bisphenylamine-Appended Benzocarcogendiazole Fluorophores.

Benzocarcogendiazole units have been frequently utilized for optoelectronics such as organic solar cells because of their robustness, rigidity, and band-gap tunability based on their strong electron-withdrawing properties. Focusing on the luminescent characteristics, these molecules have been utilized to demonstrate highly sensitive chromisms because of the potential of charge transfer. Here, we demonstrate deep red-emissions in bis(4-tert-butylphenyl)amine-appended benzocarcogendiazole-based donor-acceptor-donor (D-A-D) fluorophores, namely 1 and 2. Because benzocarcogendiazole and bis(4-tert-butylphenyl)amine serve as strong electron acceptor and donor, respectively, strong intramolecular charge transfer (ICT) enables long wavelength of photoluminescence (PL) even in the small molecular weight. Although photoluminescence (PL) in long wavelength tends to exhibit quite low absolute PL quantum efficiency (ΦPL), the values of solutions 1 and 2 are quite high (up to 50 %). According to X-ray crystallographic characterizations and DFT calculations, these high ΦPL values are attributable to the segregated π-planes of benzocarcogendiazole units, which is induced by the bulky substituents of bis(4-tert-butylphenyl)amines.

N-Halosuccinimide-CeCl3 Transient Charge-Transfer Complexes as Semi Heterogeneous Photocatalyst in Cyclization of N-Propargylamides.

In this work, we used photoinert anhydrous cerium(III) chloride, to form a transient charge-transfer (CT) complex with NXS (N-bromosuccinimide or NBS and N-iodosuccinimide or NIS) in acetonitrile. These transient CT complexes acted as a semi-heterogeneous photocatalyst. These complexes allowed the Ce(III) ions to absorb light, turning them into strong electron donors that transferred electrons to NXS. This created halide radicals from NXS radical anions, helping to turn N-propargylamides into oxazole aldehydes. Experiments with DMPO and spin-trapping showed that a radical-based mechanism followed a single electron transfer (SET) pathway. Notably, CeCl3 was reused after the reaction without much decomposition, as it was regenerated and separated through simple filtration.

Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza-Hetero Aromatic Compounds.

Excited states of radical anions derived from the photoreduction of stable organic molecules are suggested to serve as potent reductants. However, excited states of these species are too short-lived to allow bimolecular quenching processes. Recently, the singlet excited state of Meisenheimer complexes, which possess a long-lived excited state, was identified as the competent species for the reduction of challenging organic substrates (-2.63 V vs. SCE, saturated calomel electrode). To produce reasonably stable and simply accessible different Meisenheimer complexes, the addition of nBuLi to readily available aromatic heterocycles was investigated, and the photoreactivity of the generated species was studied. In this paper, we present the straightforward preparation of a family of powerful photoreductants (*Eox<-3 V vs. SCE in their excited states, determined by DFT and time-dependent TD-DFT calculations; DFT, density functional theory) that can induce dehalogenation of electron-rich aryl chlorides and to form C-C bond through radical cyclization. Photophysical analyses and computational studies in combination with experimental mechanistic investigations demonstrate the ability of the adduct to act as a strong electron donor under visible light irradiation.

Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Hetero Aromatic Compounds

AbstractExcited states of radical anions derived from the photoreduction of stable organic molecules are suggested to serve as potent reductants. However, excited states of these species are too short‐lived to allow bimolecular quenching processes. Recently, the singlet excited state of Meisenheimer complexes, which possess a long‐lived excited state, was identified as the competent species for the reduction of challenging organic substrates (−2.63 V vs. SCE, saturated calomel electrode). To produce reasonably stable and simply accessible different Meisenheimer complexes, the addition of nBuLi to readily available aromatic heterocycles was investigated, and the photoreactivity of the generated species was studied. In this paper, we present the straightforward preparation of a family of powerful photoreductants (*Eox&lt;−3 V vs. SCE in their excited states, determined by DFT and time‐dependent TD‐DFT calculations; DFT, density functional theory) that can induce dehalogenation of electron‐rich aryl chlorides and to form C−C bond through radical cyclization. Photophysical analyses and computational studies in combination with experimental mechanistic investigations demonstrate the ability of the adduct to act as a strong electron donor under visible light irradiation.

Thiourea enhanced oxidase-like activity of CeO2/CuxO nanozyme for fluorescence/colorimetric detection of thiourea and glutathione

A novel fluorescence/colorimetric dual-mode sensor, based on enhancement of the oxidase-like activity of CeO2/CuxO nanozyme towards the oxidation of o-phenylenediamine (OPD) induced by thiourea (TU), has been proposed for TU detection. The catalytic activity enhancement on CeO2/CuxO can be attributed to the strong electron-donation ability of TU, which promoted hydroxyl radical generation and amplified OPD oxidization with enhanced dual-signal readout. By integrating a portable paper-chip and smartphone system, this CeO2/CuxO-OPD system achieved on-site visual colorimetric analysis of TU. The dual-mode sensor demonstrated high sensitivity and specificity in recognizing TU, with a detection limit (LOD) of 1.90 μM and a linear range (LR) 2.5–80 μM in fluorescent mode; as well as an LOD of 6.69 μM and an LR 10–250 μM in colorimetric mode. Furthermore, the CeO2/CuxO-TU-OPD system has been designed for dual-mode glutathione (GSH) detection with enhanced sensitivity, achieving an LOD of 0.19 μM and an LR 0.5–10 μM in fluorescent mode; as well as an LOD of 1.24 μM and an LR 1.25–25 μM in colorimetric mode. Additionally, GSH discrimination (fluorescent mode) was successfully achieved in different biological samples, showing good consistency with the standard method. The recoveries ranged from 96.8 % to 116.7 % in serum samples and from 97.3 % to 107.7 % in cell lysates, with RSDs less than 2 %. This work not only introduced a novel approach to enhance oxidase-like activity of nanozymes but also provided an efficient field-suitable tool for enhanced dual-mode response towards TU and GSH.

Pt‐Sn/Sb Interaction Induces Reversed Charge Transfer and Selective Hydroxyl Adsorption for Enhanced Hydrogen Electro‐Oxidation

AbstractThe challenges encountered by Pt‐based electrocatalysts in alkaline hydrogen oxidation reaction include high Pt dosage and conflicting demands for modulating adsorption strengths among diverse intermediates. Here, an ultrasmall Pt cluster grafted on antimony tin oxide nanocrystalline with strong electron donor ability to minimal Pt dosage yet maximized electrocatalytic performance is developed. Mechanism studies show that the formation of Pt–Sn/Sb interaction at the heterointerface and the resultant reversed electron transfer selectively enhance the adsorption for OH‐ while concurrently weakening the binding strength for *H and CO toward Pt clusters. This accelerates the kinetics of H2/CO oxidation by promoting the binding of OH species with *H/*CO, yielding the catalyst with up to 5.7‐fold higher mass‐specific activity than benchmark Pt/C and increased resistance to CO poisoning. This work demonstrates the rational design of the synergistic multi‐site interactions towards advanced Pt‐based catalysts.

Silicon Clathrate-Supported Catalysts with Low Work Functions for Ammonia Synthesis.

Diamond-type silicon has a work function of ≈4.8eV, and conventional n- or p-type doping modifies the value only between 4.6 and 5.05eV. Here, it is shown that the alkali clathrates AxSi46 have substantially lower work functions approaching 2.6eV, with clear trends between alkali electropositivity and clathrate cage size. The low work function enables alkali clathrates such as K8Si46 to be effective Haber-Bosch catalyst supports for NH3 synthesis. The catalytic properties of Si, Ge, and Sn-based clathrates are investigated while supporting Fe and Ru on the surface. The activity largely scales with the work function, and low activation energies below 60kJ mol-1 are observed due to strong electron donation effects from the support. Ru metal and Sn clathrates seem to be unsuitable for stability issues. Compared to other similar hydride/electride catalysts, the simple structure and composition combined with stability in air/water make a systematic study of these clathrates possible and open the door to other electron-rich Zintl phases and related intermetallics as low-work function materials suitable for catalysis. The observed low work function may also have implications for other existing electronic applications.

A turn-off xanthene-based fluorescent probe for detection of cysteine and its practical application in bioimaging and food samples

BackgroundCys, as an essential amino acid that can be ingested from daily food, plays an important role in maintaining the oxidative balance in cells. Abnormal Cys levels in organisms will lead to various diseases. Therefore, it is of great significance to construct a fluorescent probe that can detect Cys levels in food and biological systems. ResultsHere, a turn-off type probe TA had been successfully synthesized, which attached diethylamine as the strong electron donor, acrylate as the weak electron donor, and xanthene as the π-bridge. TA showed wonderful selectivity, low detection limit, good photostability and well live-cell compatibility for Cys by reducing acrylate group to hydroxyl group of TAOH. The reaction mechanism was demonstrated by 1H NMR, ESI-MS spectra, pH-dependent response experiments, and DFT calculations. Importantly, the reason why TAOH exhibited no fluorescence was the disappearance of the ICT effect in the molecule due to the dominant existence of spirocyclic state of TAOH. In addition, the probe can be used not only for the imaging detection of Cys in A549 cells and zebrafish, but also for the detection of Cys levels in food samples. SignificanceThis work provides a new idea for the design of Cys fluorescent probe, which may be beneficial to the comprehension of the potential mechanism of novel fluorescent probe.

Mechanical-energy-driven HCHO purification with lattice distortion engineering and surface grafting

Formaldehyde (HCHO) is a typical indoor air pollutant with high toxicity and wide distribution. It is of great significance to use clean energy for efficient catalytic oxidation of HCHO. In this work, Fe-doped bismuth titanate (Bi4Ti3O12) nanosheets with polyethyleneimine (PEI) grafting were prepared, exhibiting a remarkable complete elimination of HCHO under ultrasonic vibration. Piezocatalytic mechanism analysis revealed that Fe3+ doping induced lattice distortion and accelerated the transfer of electrons through valence change. Additionally, the abundant amino groups in PEI efficiently gathered formaldehyde molecules on the surface of the catalysts for next catalytic reaction as well as accelerate the separation of carriers by trapping holes as strong electron donors. It showed an effective strategy for degrading organic pollutants in the air with adsorption-enhanced piezocatalysts driven by mechanical energy.

Ultrafast response of diketo-pyrrolo-pyrrole dyes with large two-photon absorption enhancement as well as AIE property

To study the effect of terminal groups substituent on the two-photon absorption (TPA) properties of [Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text] structural dyes with diketo-pyrrolo-pyrrole (DPP) as central electron acceptor group, linear/transient absorption spectroscopy, one/two-photon fluorescence spectra, open-aperture [Formula: see text]-scan, and excited states quantum chemical calculations have been performed to systematically study the intermediate product electron acceptor J0 as well as three [Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text]-[Formula: see text] structural dyes using benzene, triphenylamine and 2,3-methoxy-triphenylamine as terminal electron donors, named as J1, J2, and J3, respectively. The intermediate product electron acceptor itself exhibits a relatively large TPA response, which indicates the DPP group has a large conjugated system. J2, with strong electron-donating ability groups triphenylamine as terminal groups, shows a large TPA cross-section of 534[Formula: see text]GM, which is approximately 10 times larger than that of J1 with weak electron pushing/pulling abilities groups benzene as terminal groups (51[Formula: see text]GM). The result indicates that the electron-donating abilities of terminal groups do play a key role in TPA response. Furthermore, methoxy substituent on the terminal triphenylamine groups can further effectively increase the TPA response, J3exhibits a 15-fold enhancement compared with that of J1. Transient absorption spectra and quantum chemical calculation results are well accorded with the experimental results. Terminal substituents with strong electron donor groups are beneficial for the formation of intramolecular charge transfer (ICT) process. Besides, methoxy substituent in the terminal of triphenylamine groups can further enhance the degree of ICT and induce AIE characteristics in the molecule.

Transformation of by-product silicon tetrachloride to an efficient and stable heterogeneous base catalyst: Valorization of glycerol into valuable glycerol carbonate

The by-product silicon tetrachloride (SiCl4) from the polysilicon industry was recycled to fabricate a highly efficient and stable lithium silicate (LS) catalyst for upgrading of oversupplied biodiesel by-product glycerol to valuable glycerol carbonate (GC). The characteristics of the LS catalyst were systematically investigated by various experimental characterization techniques and density functional theory (DFT) calculations. The experimental results showed that the hydrolysis of SiCl4 in the lithium nitrate solution helping to the solid phase synthesis of the LS catalyst as lithium could be uniformly dispersed in the silica gel. The as-synthesized LS catalyst mainly consists of lithium orthosilicate with strong basic sties, favoring the catalytic conversion of glycerol. The LS catalyst exhibited an appreciably high catalytic efficiency (turnover frequency of 2.72 min−1) and glycerol conversion (99.8±1.8 %) compared to other reported solid base catalysts. The apparent activation energy (Ea) of this reaction was calculated to be 39.51 kJ/mol. Further, benefiting from the stable silicate structure, the LS catalyst showed an enhanced catalytic stability as the glycerol conversion declined less than 5 % after five times reuse without regeneration. The LS catalyst also revealed marked resistance to the solid base catalyst poisons like water and methanol compare to that of commercial calcium-based catalyst. The temperature-programmed desorption of CO2 (CO2-TPD) and DFT results affirmed that the low-coordination lattice oxygen of the isolated SiO4 tetrahedron on the surface of the LS catalyst acting as a strong basic electron donor promoted the transesterification reaction between DMC and glycerol. As a result, the SiCl4-derived LS catalyst possessed remarkable catalytic efficiency and reusability, which could be an ideal candidate to meet the requirements for industrial application and highlight the potential application of the by-product SiCl4.

Synthesis, Electrochemistry and Photochemistry of Hypervalent Phosphorus(V) Porphyrin and Antimony(V) Porphyrin Black Dyes

In the last few years, our focus has been on push-pull type hypervalent Group 15 porphyrins with intramolecular charge transfer (ICT) properties. Insertion of P(V) or Sb(V) ion in the porphyrin cavity results in a highly electron-deficient porphyrin center, under this condition the presence of electron-rich units in porphyrin meso-positions results in charge transfer within the molecules. Recently, we extended this strategy to 5,10,5,20-tetrakis(triphenylamine)porphyrin derivative where strong electron donor triphenylamine (TPA) units are in meso-positions. Upon insertion of the P(+5) and Sb(+5) ion, the resulting hypervalent Group 15 porphyrins manifested a strong ICT from the TPA units to the central porphyrin ring. The existence of ICT makes the absorption profiles cover the entire visible region with high molar extinction coefficients. Due to this reason, the studied hypervalent Group 15 porphyrins appear as black dyes. Here, I will present these porphyrins and discuss their structural, redox, and remarkable photophysical properties. Figure 1