Electron-rich Core Research Articles

Structural insights into 1,4-bis(neopentyloxy)pillar[5]arene and the pyridine host–guest system

The crystal structure of 1,4-bis(neopentyloxy)pillar[5]arene, C95H140N2O10 (TbuP), featuring two encapsulated pyridine molecules, reveals significant host–guest interactions. Interestingly, the pyridine guests are positioned near the neopentyloxy substituents instead of the electron-rich aromatic core of the pillar[5]arene. This spatial arrangement suggests a preference for the pyridine molecules to engage with the aliphatic regions of the host. Detailed analysis of the structural characteristics of this host–guest system (TbuP·2Py), as well as its packing pattern within the crystal network, is presented and discussed.

Advancing Fab-Compatible Color-Selective Organic Photodiodes: Tailored Molecular Design and Nanointerlayers.

High-performance organic photodiodes (OPDs) and OPD-based image sensors are primarily realized using solution processes based on various additives and coating methods. However, vacuum-processed OPDs, which are more compatible with large-scale production, have received little attention, thereby hindering their integration into advanced systems. This study introduces innovations in the material and device structures to prepare superior vacuum-processed OPDs for commercial applications. A series of vacuum-processable, low-cost p-type semiconductors is developed by introducing an electron-rich cyclopentadithiophene core containing various electron-accepting moieties to fine-tune the energy levels without any significant structural or molecular weight changes. An additional nanointerlayer strategy is used to control the crystalline orientation of the upper-deposited photoactive layer, compensating for device performance reduction in inverted, top-illuminated OPDs. These approaches yielded an external quantum efficiency of 70% and a specific detectivity of 2.0 × 1012 Jones in the inverted structures, which are vital for commercial applications. These OPDs enabled visible-light communications with extremely low bit error rates and successful X-ray image capture.

Gallium-based liquid metals as reaction media for nanomaterials synthesis.

Gallium-based liquid metals (LMs) and their alloys have gained prominence in the realm of flexible and stretchable electronics. Recent advances have expanded the interest to explore the electron-rich core and interface of LMs to synthesize various nanomaterials, where Ga-based LMs serve as versatile reaction media. In this paper, we delve into the latest developments within this burgeoning field. Our discussion begins by elucidating the unique attributes of LMs that render them suitable as reaction media, including their high metal solubility, low standard reduction potential, self-limiting oxidation and ultra-smooth and "layer" surface. We then provide a comprehensive categorized summary of utilizing these features to fabricate a variety of nanomaterials, including pure metallic materials (metal alloys, metal crystals, porous metals, high-entropy alloys and metallic single atoms), metal-inorganic compounds (2D metal oxides, 2D metallic inorganic compounds and 2D graphitic materials), as well as metal-organic composites (metal-organic frameworks). This paper concludes by discussing the current challenges in this field and exploring potential future directions. The versatility and unique properties of Ga-based LMs are poised to play a pivotal role in the future of nanomaterial science, paving the way for more efficient, sustainable, and innovative technological solutions.

Quadrupolar, Highly Polarized Dyes: Emission Dependence on Viscosity and Selective Mitochondria Staining.

Quadrupolar A-D-A-type 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) bearing pyridinium and quinolinium substituents emit in the 500-600 nm region. The enhancement of electronic communication between the electron-rich heterocyclic core and electron-deficient peripheral substituents turned out to be crucial for achieving emission enhancement in viscous media. DHPP bearing two 4-pyridinium substituents has optical brightness 34,000 in glycerol and only 700 in MeOH, as evidenced by measurements of the emission intensity and fluorescence lifetimes in a series of polar solvents. Such behavior makes it an excellent candidate for viscosity probes in fluorescence microscopy, as demonstrated by the fluorescence imaging of H9C2 cardiomyocytes.

Enhanced Hole Mobility of p-Type Materials by Molecular Engineering for Efficient Perovskite Solar Cells.

Star-shaped triazatruxene derivative hole-transporting materials (HTMs), namely, 3,8,13-tris(4-(8a,9a-dihydro-9H-carbazol-9-yl)phenyl)-5,10,15-trihexyl-10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazole (TAT-TY1) and 3,8,13-tris(4-(8a,9a-dihydro-9H-carbazol-9-yl)phenyl)-5,10,15-trihexyl-10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazole (TAT-TY2), containing electron-rich triazatruxene cores and donor carbazole moieties, were synthesized and successfully used in triple-cation perovskite solar cells. All the HTMs were obtained from relatively inexpensive precursor materials using well-known synthesis procedures and uncomplicated purification steps. All the HTMs, including the 5,10,15-trihexyl-10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazole (TAT-H) main core, had suitable highest occupied molecular orbitals (HOMOs) for perovskite (TAT-H: -5.15 eV, TAT-TY1: -5.17 eV, and TAT-TY2: -5.2 eV). Steady-state and time-resolved photoluminescence results revealed that hole transport from the valence band of the perovskite into the HOMO of the new triazatruxene derivatives was more efficient than with TAT-H. Furthermore, the substitution of n-hexylcarbazole and 9-phenylcarbazole in triazatruxene altered the crystalline nature of the main core, resulting in a smooth and pinhole-free thin-film morphology. As a result, the hole mobilities of TAT-TY1 and TAT-TY2 were measured to be one order of magnitude higher than that of TAT-H. Finally, TAT-TY1 and TAT-TY2 achieved power conversion efficiencies of up to 17.5 and 16.3%, respectively, compared to the reference Spiro-OMeTAD. These results demonstrate that the new star-shaped triazatruxene derivative HTMs can be synthesized without using complicated synthesis strategies by controlling the intrinsic morphology of the TAT-H main core.

The deeper it goes, the brighter it glows: NIR emissive nitro-terrylene diimides with deep LUMOs.

Herein, we present the first examples of air-stable, deep-lowest unoccupied molecular orbital (LUMO) polycyclic aromatic molecules with emission in the near-infrared (NIR) region, using nitration as a strategy. Despite the fact that nitroaromatics are non-emissive, the choice of a comparatively electron-rich terrylene core proved to be beneficial for achieving fluorescence in these molecules. The extent of nitration proportionately stabilized the LUMOs. Tetra-nitrated terrylene diimide exhibited a deep-LUMO (≤-4.5 eV) of -5.0 eV vs. Fc/Fc+, the lowest for any larger RDIs. These are also the only examples of emissive nitro-RDIs, with larger quantum yields.

The magic of biaryl linkers: the electronic coupling through them defines the propensity for excited-state symmetry breaking in quadrupolar acceptor-donor-acceptor fluorophores.

Charge transfer (CT) is key for molecular photonics, governing the optical properties of chromophores comprising electron-rich and electron-deficient components. In photoexcited dyes with an acceptor-donor-acceptor or donor-acceptor-donor architecture, CT breaks their quadrupolar symmetry and yields dipolar structures manifesting pronounced solvatochromism. Herein, we explore the effects of electronic coupling through biaryl linkers on the excited-state symmetry breaking of such hybrid dyes composed of an electron-rich core, i.e., 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP), and pyrene substituents that can act as electron acceptors. Experimental and theoretical studies reveal that strengthening the donor-acceptor electronic coupling decreases the CT rates and the propensity for symmetry breaking. We ascribe this unexpected result to effects of electronic coupling on the CT thermodynamics, which in its turn affects the CT kinetics. In cases of intermediate electronic coupling, the pyrene-DHPP conjugates produce fluorescence spectra, spreading over the whole visible range, that in addition to the broad CT emission, show bands from the radiative deactivation of the locally excited states of the donor and the acceptors. Because the radiative deactivation of the low-lying CT states is distinctly slow, fluorescence from upper locally excited states emerge leading to the observed anti-Kasha behaviour. As a result, these dyes exhibit white fluorescence. In addition to demonstrating the multifaceted nature of the effects of electronic coupling on CT dynamics, these chromophores can act as broad-band light sources with practical importance for imaging and photonics.

Silver Nanoparticle-Incorporated Defect-Engineered Zr-based Metal-Organic Framework for Efficient Multicomponent Catalytic Reactions.

Small-sized silver nanoparticles are incorporated into a thiol-functionalized stable Zr-based metal-organic framework (MOF). Thiol functionalization has been carried out using 2-mercapto benzoic acid (2-MBA) as the modulator, which promotes defect formation in the MOF structure. The incorporation of silver nanoparticles aided by the silver-sulfur interactions in this defective MOF gives rise to catalytic activity. Its catalytic efficiency in the highly atom-efficient A3 coupling reaction has been studied for a variety of substrates with impressive recyclability. The synergistic effect of the electron-rich silver core and electron-deficient surface of the thiol-bonded silver nanoparticle is key for this catalytic reaction.

Mechanism of high- and low-valence doping on adsorbed oxygen of SnO2-based gas sensors and a strategy to combine the advantages of both dopants

The effect of high- and low-valence doping on adsorbed oxygen has been studied and intensely discussed for decades, in which the high-valence dopant can provide more electrons for ionosorbed oxygen species while low-valence dopant can provide more adsorption sites. In this work, this effect is observed directly by Quasi in-situ X-ray photoelectron spectroscopy and CO temperature-programmed reduction, and rationalized by density functional theory calculations. It is found that the oxygen vacancies can be easier to generate on Co-doped SnO2 surface, but the decrease in surface electron concentration actually reduces the amount of adsorbed oxygen at working temperature while Sb-doped SnO2 is more conducive to oxygen adsorption but the enormous electron concentration makes the resistance variation caused by the surface reactions insignificant. In order to combine the advantages of both dopants, Sb-doped SnO2@Co-doped SnO2 core-shell structure are designed and prepared. The synergism of the core and shell can enhance sensing reactions on the surface while efficiently converting the surface reactions into a resistance change. On the one hand, the electron diffusion from the electron-rich core to the shell provides the electrons required for oxygen adsorption, which ensures sufficient surface reactions. On the other hand, a potential barrier is formed between the core and shell which can regulate electron transport between adjacent cores, thereby effectively converting the surface reaction into a resistance change.

Over 1000 nm photoresponse with cyclopentadithiophene-based non-fullerene acceptors for efficient organic solar cells

Non-fullerene acceptors have a pivotal role in the progress of organic solar cells (OSCs). Though, optical characteristics most of NFAs is quite limited within the range of 600–900 nm, limiting the short-circuit density (Jsc) of the OSCs devices. To address this issue, we have designed nine different C-shaped cyclopentadithiophene (CPDT)-based acceptor–donor-acceptor (A-D-A) structured NFAs for OSCs. To this end, various end-cap functional units have been used to further modify the reference molecule (C0) to improve the optoelectronics and photophysical characteristics of these materials. For this, various advanced quantum mechanical density functional theory (DFT) and time dependent (TD-DFT) approached used to explore the hidden potential of these materials (R, CA1-CA9). The characterizations associated with frontier molecular orbitals (FMOs), transition density Matrix (TDM) analysis, open-circuit voltages (Voc), electron-hole reorganizational energies, fill factor and optical properties of all the investigated molecules are calculated at DFT and TD-DFT-B3LYP/6-31G. In addition to all these calculations the PTB7-Th:C5 complex study (D:A) has also been investigated to check out the charge-transfer from donor polymer (PTB7-Th) to NFA C5 at the D:A interface. The results of these investigations reveal that all the designed A-D-A molecules (C1-C9) with electron-rich core and with electron-deficient end-capped acceptors are perfect for efficient tuning of optical and electrical parameters. With such approach, we can design desired photovoltaic materials by tuning their FMO energy levels, binding energy, and reorganizational energies, Voc, fill factor and absorption maxima characteristics. Therefore, these deigned materials (C1-C9) are highly recommended for synthesis to develop an efficient OSCs. And, this approach could be use effectively to design desire properties materials for the future development of an efficient photovoltaic materials.

Enhancing the Intermolecular Interactions of Ladder-Type Heteroheptacene-Based Nonfullerene Acceptors for Efficient Polymer Solar Cells by Incorporating Asymmetric Side Chains

Enhancing the Intermolecular Interactions of Ladder-Type Heteroheptacene-Based Nonfullerene Acceptors for Efficient Polymer Solar Cells by Incorporating Asymmetric Side Chains

Conjugated Extension of Non-Fullerene Acceptors Enables Efficient Organic Solar Cells with Optoelectronic Response over 1000 nm

The efficient near-infrared response of light-active materials is one of the prerequisites for the most advanced organic solar cells (OSCs). Two benzodithiophene fused-ring cores (BT-4T and DBT-4T), featured with stepwise enlarged conjugations and improved electron-donor characteristics, are designed and used as the central donor units for the construction of acceptor–donor–acceptor-type molecules ZB8 and ZB10. The significantly enhanced intramolecular charge transfer endows ZB8- and ZB10-based OSCs with a photoelectronic response over 1000 nm. With more favorable molecular energy levels and an asymmetric configuration, ZB8-based best OSCs afford a 12.30% power conversion efficiency, better than that of 11.08% for the ZB10-based one. Our successful exploration for electron-rich fused-ring cores provides a quite rare but promising platform for highly efficient OSCs with a photoelectronic response over 1000 nm.

Phenalene—A New Ring-Locked Vinyl Bridge for Nonfullerene Acceptors With Enhanced Chemical and Photochemical Stabilities

Currently, the two exocyclic vinyl bridges in the acceptor–donor–acceptor (A–D–A)-type nonfullerene acceptors (NFAs) have been widely recognized as one of the most vulnerable sites under external stresses. Embedding the exocyclic vinyl bridges into an aromatic ring could be a feasible solution to stabilize them. Herein, we successfully develop a phenalene-locked vinyl bridge via a titanium tetrachloride—pyridine catalytic Knoevenagel condensation, to synthesize two new A–D–A-type unfused NFAs, EH-FPCN and O-CPCN, wherein malononitrile is used as the electron-deficient terminal group while fluorene and carbazole rings are used as the electron-rich cores, respectively. These two NFAs possess wide bandgaps associated with deep energy levels, and significantly enhanced chemical and photochemical stabilities compared to the analogue molecule O-CzCN with normal exocyclic vinyl bridges. When pairing with a narrow bandgap polymer donor PTB7-Th, the fabricated EH-FPCN- and O-CPCN-based organic solar cells achieved power conversion efficiencies of 0.91 and 1.62%, respectively. The higher efficiencies for O-CPCN is attributed to its better film morphology and higher electron mobility in the blend film. Overall, this work provides a new design strategy to stabilize the vulnerable vinyl bridges of A–D–A-type NFAs.

Pt(ii)-coordinated tricomponent self-assemblies of tetrapyridyl porphyrin and dicarboxylate ligands: are they 3D prisms or 2D bow-ties?

Thermodynamically favored simultaneous coordination of Pt(ii) corners with aza- and carboxylate ligands yields tricomponent coordination complexes with sophisticated structures and functions, which require careful structural characterization to paint accurate depiction of their structure–function relationships. Previous reports claimed that heteroleptic coordination of cis-(Et3P)2PtII with tetrapyridyl porphyrins (M′TPP, M′ = Zn or H2) and dicarboxylate ligands (XDC) yielded 3D tetragonal prisms containing two horizontal M′TPP faces and four vertical XDC pillars connected by eight Pt(ii) corners, even though such structures were not supported by their 1H NMR data. Through extensive X-ray crystallographic and NMR studies, herein, we demonstrate that self-assembly of cis-(Et3P)2PtII, M′TPP, and four different XDC linkers having varied lengths and rigidities actually yields bow-tie (⋈)-shaped 2D [{cis-(Et3P)2Pt}4(M′TPP) (XDC)2]4+ complexes featuring a M′TPP core and two parallel XDC linkers connected by four heteroleptic PtII corners instead of 3D prisms. This happened because (i) irrespective of their length (∼7–11 Å) and rigidity, the XDC linkers intramolecularly bridged two adjacent pyridyl-N atoms of a M′TPP core via PtII corners instead of connecting two cofacial M′TPP ligands and (ii) bow-tie complexes are entropically favored over prisms. The electron-rich ZnTPP core of a representative bow-tie complex selectively formed a charge-transfer complex with highly π-acidic 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-heaxacarbonitrile but not with a π-donor such as pyrene. Thus, this work not only produced novel M′TPP-based bow-tie complexes and demonstrated their selective π-acid recognition capability, but also underscored the importance of proper structural characterization of supramolecular assemblies to ensure accurate depiction of their structure–property relationships.

Ionothermal synthesis of phosphonitrilic-core covalent triazine frameworks for carbon dioxide capture

Covalent Triazine Frameworks (CTFs) are a class of porous organic frameworks with tunable properties obtainable through rational design targeting a wide range of applications. In the present work, we developed a series of CTFs with phosphazene core for CO2 adsorption. The CTFs were synthesized using building blocks of hexakis(oxy)hexabenzonitrile phosphazene (HCPz) under ionothermal conditions and ZnCl2 as catalyst. The effect of ZnCl2/monomer ratio and the ionothermal reaction temperature and synthesis procedure on the porosity of the Pz-CTFs were systematically explored. The Pz-CTF synthesized using a molar ratio of ZnCl2/monomer of 10 with gradient ionothermal reaction conditions (400 °C/25 h; 450 °C/13 h; 500 °C/1h; 600 °C/1h) yielded an amorphous, predominantly ultra-microporous material (Pz-CTF6) with high surface area (SBET of 1009 m2 g−1). The primary aspect of the applied gradient ionothermal reaction scheme is that it induces a simultaneous reversible and irreversible trimerization of nitriles, allowing restructuring of the triazine units, thus resulting in an extended microporous network. Besides, the highly crosslinked, electron-rich phosphazene core provided high structural and thermal stability (up to 500 °C) and enhanced CO2-philicity of the synthesized CTFs. As a result, Pz-CTF6 showed a CO2 uptake capacity of 4.19 and 2.47 mmol g−1 at 273 and 298 K, respectively, at 1 bar. In addition, it exhibited a high CO2/N2 selectivity of 147 for a feed containing 85% of CO2 at 50 mbar and 298 K, as determined by the IAST method. Furthermore, the developed adsorbents exhibited enhanced hydrophobicity, causing a rather mild reduction in CO2 capacity when humidity conditions were applied. These findings show that the synthesized Pz-CTFs are promising for CO2 capture and adsorptive separation.

Boosting the photovoltaic performance of ladder-type heteroheptacene-based nonfullerene acceptors by incorporating auxochromic groups in the electron-rich core

Nonfullerene acceptors (NFAs) that efficiently harvest sunlight and transport the consequent charge are key to advancing the performance of polymer solar cells (PSCs). Herein we demonstrate that the NFA with alkylthio side-chains incorporated in the heteroheptacene core (MS1) shows a significantly increased molar extinction coefficient and enhanced molecular ordering in comparison with the counterpart with alkyl side-chains (MC1). Therefore, in combination with a benchmark donor polymer (PM6), the resulting MS1-based PSC shows an enhanced power conversion efficiency (PCE) of 14.13% with a fill factor (FF) of 71.66% and a short-circuit current density (Jsc) of 21.70 mA cm−2 comparing with the MC1-based PSC which shows a PCE of 11.87% with a FF of 62.55% and a Jsc of 20.39 mA cm−2. The enhanced photovoltaic performance for the MS1-based PSC can be in part attributed to the increased light-harvesting ability of the MS1-based active layer and in part attributed to its boosted carrier mobilities and reduced charge recombination. Moreover, with an electrode optimization, the best-performing MS1-based PSC shows a further enhanced PCE of 15.01% which is an impressive efficiency among all acceptor–donor–acceptor type NFAs reported to date. This work suggests the important role of the auxochromic groups in the electron-rich core in determining the photovoltaic performance of NFAs.

Design of All-Fused-Ring Electron Acceptors with High Thermal, Chemical, and Photochemical Stability for Organic Photovoltaics

High-performance donor–acceptor electron acceptors containing 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN)-type terminals are labile toward photooxidation and basic conditions, and ...

Carbon-Bridged 1,2-Bis(2-thienyl)ethylene: An Extremely Electron Rich Dithiophene Building Block Enabling Electron Acceptors with Absorption above 1000 nm for Highly Sensitive NIR Photodetectors.

The emerging donor-acceptor-donor (A-D-A)-type nonfullerene acceptors (NFAs) featuring near-infrared (NIR) photoresponsivity have greatly boosted the development of organic photovoltaics (OPVs) and display great potential for sensitive NIR organic photodetectors (OPDs). However, NIR NFAs with absorption above 1000 nm, which is of great importance for application in NIR OPDs for bioimaging, remote communication, night surveillance, etc., are still rare due to the scarcity of strong electron-rich cores. We report herein a new dithiophene building block, namely PDT, which exhibits the strongest electron-donating ability among the widely used dithiophene building blocks. By applying PDT and PDTT as the electron-donating cores and DFIC as the electron-accepting terminals, we developed two new NIR electron acceptors, PDTIC-4F and PDTTIC-4F, with optical absorptions up to 1030 nm, surpassing that of the well-known O6T-4F acceptor. In comparison with the carbon-oxygen-bridged core COi8 in O6T-4F, the synthetic complexity of PDT and PDTT is significantly reduced. Conventional OPV devices based on PM6:PDTTIC-4F display power conversion efficiencies (PCEs) of up to 10.70% with a broad external quantum efficiency (EQE) response from the ultraviolet-visible to the infrared, leading to a high short-circuit current density (Jsc) of 25.90 mA cm-2. Encouraged by these results, we investigated inverted PM6:PDTTIC-4F-based OPD devices by suppressing the dark current via modulation of the film thickness. The optimal OPD device exhibits compelling performance metrics that can compete with those of commercial silicon photodiodes: a record responsivity of 0.55 A W-1 (900 nm) among photodiode-type OPDs and excellent shot-noise-limited specific detectivity (Dsh*) of over 1013 jones.

High-Performance Ternary Polymer Solar Cells Enabled by a New Narrow Bandgap Nonfullerene Small Molecule Acceptor with a Higher LUMO Level.

Obtaining a large open-circuit voltage (VOC ) and high short-circuit current density (JSC ) simultaneously is important in improving power conversion efficiency (PCE) of organic photovoltaics. The ternary strategy with using a higher lowest unoccupied molecular orbital (LUMO) level nonfullerene acceptor (NFA) guest can achieve increased VOC , yet JSC is decreased or maintained, so it's still a challenge to offer increased VOC and JSC values concurrently via the newly presented VOC -increased ternary strategy. To overcome this issue, a new narrow bandgap NFA TT-S-4F is reported by introducing 3,6-dimethoxylthieno[3,2-b]thiophene (TT) as π-spacers to connect electron-rich core with terminal groups, so as to upshift the LUMO level and extend π-system. When adding 10% TT-S-4F into binary system based on PTB7-Th:IEICO-4F, the higher-LUMO-level of TT-S-4F, the increased charge mobilities, the reduced trap-assisted combination loss, and a finer nanofiber structure and increased phase separation size are obtained, which simultaneously promotes JSC , VOC , and fill factor (FF), thus obtaining an optimal PCE (12.5%vs 11.5%). This work illustrates that an extending conjugated backbone with large π-spacers and inclusion of alkylthiophenyl side-chains is a concept to synthesize NFA guests for use on the VOC -increased ternary strategy that enables to realize simultaneously increased JSC , VOC , and FF.

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging.

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP)n (n=1-3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40-0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δTPA values of TAT-(ZnP)2 and TAT-(ZnP)3 further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D-π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D-π-A-D multipolar array.