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Combined photodynamic and photothermal therapy (PDT and PTT) can achieve more superior therapeutic effects than the sole mode by maximizing the photon utilization, but there remains a significant challenge in the development of related single-molecule photosensitizers (PSs), particularly those with type I photosensitization. In this study, self-assembly of squaraine dyes (SQs) is shown to be a promising strategy for designing PSs for combined type I PDT and PTT, and a supramolecular PS (TPE-SQ7) has been successfully developed through subtle molecular design of an indolenine SQ, which can self-assemble into highly ordered H-aggregates in aqueous solution as well as nanoparticles (NPs). In contrast to the typical quenching effect of H-aggregates on reactive oxygen species (ROS) generation, our results encouragingly manifest that H-aggregates can enhance type I ROS (â¢OH) generation by facilitating the intersystem crossing process while maintaining a high PTT performance. Consequently, TPE-SQ7 NPs with ordered H-aggregates not only exhibit superior combined therapeutic efficacy than the well-known PS (Ce6) under both normoxic and hypoxic conditions but also have excellent biosafety, making them have important application prospects in tumor phototherapy and antibacterial fields. This study not only proves that the supramolecular self-assembly of SQs is an effective strategy toward high-performance PSs for combined type I PDT and PTT but also provides a different understanding of the effect of H-aggregates on the PDT performance.
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We report an acid-mediated regulation of single-molecule junction conductance achieved using an electron-deficient unit, diazapentalene, functionalized with thiophene extending units and thiomethyl aurophilic terminal groups. This diazapentalene derivative exhibits a protonation reaction in the presence of trifluoroacetic acid, as characterized by UV-vis absorption spectroscopy, and the protonated species shows a voltage-dependent single-molecule conductance, which is not observed for the pristine molecules. Specifically, under a high bias voltage of 850 mV, we observe a conductance value for the protonated molecule larger than that for the deprotonated one by a factor of 4. Density functional theory-based transport calculations show a slight broadening of the HOMO and LUMO frontier orbitals, as well as a reduced HOMO-LUMO gap when the molecule becomes protonated; this implies an increased conductance under protonation that is consistent with the experimental conductance data. Our work demonstrates a new molecular design for versatile control of molecular conductance through the use of acid in the solvent environment.
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A key challenge in the search of new materials capable of singlet fission (SF) arises from the primary energy conservation criterion, i.e., the energy of the triplet exciton has to be half that of the singlet (E(S1) ≥ 2E(T1)), which excludes most photostable organic materials from consideration and confines the design strategy to materials with low energy triplet states. One potential way to overcome this energy requirement and improve the triplet energy is to enable a SF channel from higher energy ("hot") excitonic states (Sn) in a process called activated SF. Herein, we demonstrate that efficient activated SF is achieved in a rylene imide-based derivative acenaphth[l, 2-a]acenaphthylene diimide (AADI). This process is enabled by an increase in the energy gap to greater than 1.0 eV between the S3 and S1 states due to the incorporation of an antiaromatic pentalene unit, which leads to the emergence of anti-Kasha properties in the isolated molecule. Transient spectroscopy studies show that AADI undergoes ultrafast SF from higher singlet excited states in thin film, with excitation wavelength-dependent SF yields. The SF yield of â¼200% is observed upon higher energy excitation, and long-lived free triplets persist on the µs time scale suggesting that AADI can be used in SF-enhanced devices. Our results suggest that enlarging the Sn-S1 energy gap is an effective way to turn on the activated SF channel and shed light on the development of novel, stable SF materials with high triplet energies.
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The backwardness of n-type organic semiconductors still exists compared with the p-type counterparts. Thus, the development of high-performance n-type organic semiconductors is of great importance for organic electronic devices and their integrated circuits. In recent years, azabenzannulated perylene diimide (PDI), as one of immense bay-region-annulated PDI derivatives, has drawn considerable attentions. However, the electronic mobilities of azabenzannulated PDI derivatives are barely satisfactory. In this contribution, the peripheral benzene ring in azabenzannulated PDI 2 was fused to the ortho position by intramolecular C-H arylation cyclization. This endows the resultant azabenzannulated PDI 4 a planar configuration as well as electron deficient pentagonal ring. As a result, the electronic mobility of 4 is almost two orders of magnitude higher than that of the nonfused azabenzannulated PDI 2. This work shall pave a new avenue in elevating the performance of azabenzannulated PDI in organic electronics.
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Photoinduced symmetry-breaking charge separation (SB-CS) has been extensively observed in various oligomers and aggregates, which holds great potential for robust artificial solar energy conversion systems. It attaches great importance to the precise manipulation of interchromophore electronic coupling in realizing efficient SB-CS. The emerging studies on SB-CS suggested that it could be realized in null-excitonic aggregates, and a long-lived SB-CS state was observed, which offers an advanced platform and has gathered immense attention in the SB-CS field. Here, we unveiled the null-exciton coupling induced ultrafast SB-CS in a rigid polycyclic aromatic hydrocarbon framework, triperyleno[3,3,3]propellane triimides (TPPTI), in which three chromophores were attached through a nonconjugated bridge. Through a combination of theoretical calculations and steady-state absorption results, we demonstrated that this nonconjugated TPPTI possesses negligible exciton coupling. Increased solvent polarity was found to significantly enhance state mixing between local excited and charge transfer states. Using transient absorption spectroscopy, ultrafast SB-CS was observed in highly polar dimethylformamide, facilitated by a selective hole-transfer coupling and a favorable charge separation free energy (ΔGCS). Additionally, the rate ratio between SB-CS and charge recombination was at least high to 1800 in dimethylformamide. This investigation provides profound insights into the role of null-exciton coupling in dominating ultrafast SB-CS in multichromophoric systems.
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Aqueous zinc-ion batteries are emerging as promising sustainable energy-storage devices. However, their cyclic stability is still a great challenge due to the inevitable parasitic reaction and dendrite growth induced by water. Herein, a cosolvent strategy based on competitive effect is proposed to address the aforementioned challenges. Ethanol with a higher Gutmann donor number demonstrates lower polarity and better wettability on the Zn surface compared with water, which endows ethanol with the ability of minimizing water activity by weakening H bonds and preferentially adsorbing on the Zn electrode. The above competitive advantages synergistically contribute to inhibiting the decomposition of free water and dendrite growth. Besides, an organic-inorganic hybrid solid-electrolyte interphase layer is in situ built based on ethanol additives, where organic matrix suppresses water corrosion while inorganic fillers promote fast Zn2+ diffusion. Consequently, the electrolyte with ethanol additives boosts a high reversibility of Zn deposition, long-term durability, as well as superior Zn2+ diffusibility in both Zn half-cells (Zn||Cu and Zn||Zn batteries) and Zn full cells (Zn||PTCDA and Zn||VO2 batteries). This work sheds light on a universal strategy to design a high-reversible and dendrite-free Zn anode for stable aqueous batteries.
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The properties and formation mechanisms of the triplet state have been widely investigated since they are crucial intermediates in photo functional devices. Specifically, helical PDI dimers, horizontal expanded π-conjugated derivatives of PDI, have shown outstanding performance as electron acceptors in enhancing the performance of photovoltaics. Therefore, the exploration of triplet generation in helical PDI dimers plays a crucial role in understanding the mechanisms and excavating their further application. We make use of Se-annulation to induce intersystem crossing (ISC) in helical PDI dimers and further explore the triplet evolution process systematically as the number of Se atoms increases by transient absorption spectroscopy and the hole-electron analysis method. It shows that the twisted molecular conformation has paved the way for potential ISC in a parent molecule PDI2. The incorporation of Se atoms can result in evident promotion in the efficiency of ISC (ÏTPDI2-2Se = 96.9%) compared to the parent molecule PDI2 (ÏTPDI2 = 26.5%), indicating that chalcogen-annulation is also an efficient strategy in a π-extended system. Our results provide useful insights for understanding the triplet evolution process, which can help broaden the application of the π-extended PDI system into high-performance photovoltaics.
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The development of innovative triplet materials plays a significant role in various applications. Although effective tuning of triplet formation by intersystem crossing (ISC) has been well established in solution, the modulation of ISC processes in the solid state remains a challenge due to the presence of other exciton decay channels through intermolecular interactions. The cyclic structure of cycloparaphenylenes (CPPs) offers a unique platform to tune the intermolecular packing, which leads to controllable exciton dynamics in the solid state. Herein, by integrating an electron deficient coronene diimide (CDI) unit into the CPP framework, a donor-acceptor type of conjugated macrocycle (CDI-CPP) featuring intramolecular charge-transfer (CT) interaction was designed and synthesized. Effective intermolecular CT interaction resulting from a slipped herringbone packing was confirmed by X-ray crystallography. Transient spectroscopy studies showed that CDI-CPP undergoes ISC in both solution and the film state, with triplet generation time constants of 4.5â ns and 238â ps, respectively. The rapid triplet formation through ISC in the film state can be ascribed to the cooperation between intra- and intermolecular charge-transfer interactions. Our results highlight that intermolecular CT interaction has a pronounced effect on the ISC process in the solid state, and shed light on the use of the characteristic structure of CPPs to manipulate intermolecular CT interactions.
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Replacing the C[double bond, length as m-dash]C bond with an isoelectronic BN unit is an effective strategy to tune the optoelectronic properties of polycyclic aromatic hydrocarbons (PAHs). However, precise control of the BN orientations in large PAH systems is still a synthetic challenge. Herein, we demonstrate a facile approach for the synthesis of BN embedded perylene diimide (PDI) nanoribbons, and the polarization orientations of the BN unit were precisely regulated in the two PDI trimers. These BN doped PDI oligomers show great potential as organic cathodes for potassium-ion batteries (PIBs). In particular, trans-PTCDI3BN exhibits great improvement in voltage potential, reversible capacities (ca. 130 mA h g-1), superior rate performance (19 s to 69% of the maximum capacity) and ultralong cyclic stability (nearly no capacity decay over 30 000 cycles), which are among those of state-of-the-art organic-based cathodes. Our synthetic approach stands as an effective way to access large PAHs with precisely controlled BN orientations, and the BN doping strategy provides useful insight into the development of organic electrode materials for secondary batteries.
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Singlet fission (SF) is a spin-allowed process in which a higher-energy singlet exciton is converted into two lower-energy triplet excitons via a triplet pair intermediate state. Implementing SF in photovoltaic devices holds the potential to exceed the Shockley-Queisser limit of conventional single-junction solar cells. Although great progress has been made in exploiting the underlying mechanism of SF over the past decades, the scope of materials capable of SF, particularly polymeric materials, remains poor. SF-capable polymer is one of the most potential candidates in the implementation of SF into devices due to their distinct superiorities in flexibility, solution processability and self-assembly behavior. Notably, recent advancements have demonstrated high-performance SF in isolated donor-acceptor (D-A) copolymer chains. This review provides an overview of recent progress in the development of SF-capable polymeric materials, with a significant focus on elucidating the mechanisms of SF in polymers and optimizing the design strategies for SF-capable polymers. Additionally, the paper discusses the challenges encountered in this field and presents future perspectives. It is expected that this comprehensive review will offer valuable insights into the design of novel SF-capable polymeric materials, further advancing the potential for SF implementation in photovoltaic devices.
Assuntos
PolímerosRESUMO
Accidentally, it was found that triphenylamine (TPA) from commercial sources shows ultralong yellow-green room temperature phosphorescence (RTP) like commercial carbazole, which however disappears for lab-synthesized TPA with high purity. Herein, we for the first time identify the impurity types that cause RTP of commercial TPA, which are two N, N-diphenyl-naphthylamine isomers. Due to similar molecular polarity and very trace amount (≈0.8â , molar ratio), these naphthyl substituted impurities can be easily overlooked. We further show that even at an extremely low amount (1000000 : 1, mass ratio) of impurities, RTP emission is still generated, attributed to the triplet-to-triplet energy transfer mechanism. Notably, this doping strategy is also applicable to the triphenylphosphine and benzophenone host systems, of which strong RTP emission can be activated by simply doping the corresponding naphthyl substituted analogues into them. This work therefore provides a general and efficient host/guest strategy toward high performance and diverse organic RTP materials.
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Bay-annulated indigo (BAI) is a new potential SF-active building block, which has aroused great interest in the design of highly stable singlet fission materials. However, singlet fission of unfunctionalized BAI is inactive due to the inappropriate energy levels. Herein, we seek to develop a new design strategy by introducing the charge transfer interaction to tune the exciton dynamics of BAI derivatives. A new donor-acceptor molecule (TPA-2BAI) and two control molecules (TPA-BAI and 2TPA-BAI) were designed and synthesized to unravel the veil of CT states in tuning the excited-state dynamics of BAI derivatives. Transient absorption spectroscopy studies show that CT states are generated immediately following the excitation. However, the low-lying CT states induced by strong donor-acceptor interactions result in them acting as trap states and inhibiting the SF process. These results show that the low-lying CT state is detrimental to SF and provide insight into the design of CT-mediated BAI-based SF materials.
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Terpolymer fabrication is an effective methodology for molecular engineering and generating high-performance organic photovoltaic materials to construct highly efficient polymer solar cells. Modification of the polymer PM6 by incorporating a third component resulting in the formation of a ternary copolymer is reported to outperform PM6 in achieving enhanced device performances. However, one of the major challenges in constructing high-performance terpolymers is to counter the molecular disorder caused by the backbone entropy induced by the third moiety. In this work, double BâN bridged bipyridine (BNBP) is used as the third component, which possesses a strong out-of-plane electrostatic dipole owing to the saddle-shaped BâN fused ring structure. The out-of-plane dipole moment introduced in the modified PM6 terpolymer can be used as a means for tuning and optimizing the nanostructures of the blended films. The prepared PM6-BNBP-4 blend polymer with 4% of the benzodithiophene dione monomers replaced by BNBP results in excellent power conversion efficiency of 19.13%. This work demonstrates that the out-of-plane electrostatic dipole moment in saddle-shaped molecules is valuable for achieving high-performance organic photovoltaic donor materials.
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The vinylene-bridged helical perylene diimide (PDI) dimer (PDI2) with a build-in twisted configuration is an alternative building block to the parent PDI for the construction of efficient non-fullerene acceptor (NFAs). Moreover, it has been proved asymmetric strategy plays a vital role in the development of NFAs. Herein, we designed and synthesized a pair of acceptor-donor-acceptor (A-D-A) type PDI2 derivatives, namely IDTIC-PDI and IDT-diPDI2, which contain asymmetric and symmetric end-cap units, respectively. To determine the structure-performance relationships of asymmetric strategy, the organic solar cells (OSCs) based on these two molecules were fabricated and measured. The asymmetric IDTIC-PDI based device exhibits a much higher PCE of 8.23 % than that of symmetric IDT-diPDI2 (5.21 %). These results reveal that symmetry breaking provides an effective way to optimize the photovoltaic performances of PDI2 based OSCs.
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Materials Synthesis and Processing Polycyclic aromatic hydrocarbon (PAH) diimides are indispensable candidates for n-type organic semiconductors in organic optoelectronic devices. Developing new PAH diimide building blocks are of remarkable significance for material diversity and further advance in organic semiconductors. In this contribution, 4,5,8,9-picene diimide (PiDI) was designed and synthesized. Controllable stepwise bromination of PiDI were accomplished to afford 13-monobromo-, 13,14-dibromo-, 2,13,14-tribromo- and 2,11,13,14-tetrabromo-PiDI. Moreover, cyanation of 2,11,13,14-tetrabromo-PiDI gave the corresponding tetracyanated PiDI, which can be utilized as n-type semiconductor with OFET electron mobility up 0.073â cm2 V-1 s-1 . This result demonstrates the potential of PiDI as a building block for constructing new high-performance electronic-transporting materials.
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The development of antenna molecules with simplified structures can effectively avoid the complex exciton dynamics resulting from conformational mobility. Two distinct heterodimers TP and TBP comprising a perylenediimide (PDI) donor and terrylenediimide (TDI) acting as an energy sink were investigated. Tuned by varying functionalization positions, the bay-to-bay-linked TP offers a strong chromophore coupling, while the bay-to-N-linked TBP exhibits a weak chromophore coupling. Using transient absorption spectroscopy, we found that TP underwent ultrafast vibrational relaxation (τVR < 400 fs) from upper vibrational energy levels of the singlet states after pumping at 490 nm, and followed by electron transfer (ET, τET = 2.5 ps) from TDI to PDI. TBP exhibited ultrafast excitation energy transfer (EET, τEET = 0.48 ± 0.1 ps) from the excited PDI donor to TDI acceptor, and the subsequent charge transfer (CT) process was almost quenched. This result provides insight into designing novel small molecules capable of efficient energy transfer.
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Suppressing the photon energy loss (Eloss ), especially the non-radiative loss, is of importance to further improve the device performance of organic solar cells (OSCs). However, typical π-conjugated semiconductors possess a large singlet-triplet energy gap (ΔEST ), leading to a lower triplet state than charge transfer state and contributing to a non-radiative loss channel of the photocurrent by the triplet state. Herein, a series of triplet polymer donors are developed by introducing a BNIDT block into the PM6 polymer backbone. The high electron affinity of BNIDT and the opposite resonance effect of the BN bond in BNIDT results in a lowered highest occupied molecular orbital (HOMO) and a largely reduced ΔEST . Moreover, the morphology of the active blends is also optimized by fine-tuning the BNIDT content. Therefore, non-radiative recombination via the terminal triplet loss channels and morphology traps is effectively suppressed. The PNB-3 (with 3% BNIDT):L8-BO device exhibits both small ΔEST and optimized morphology, favoring more efficient charge transfer and transport. Finally, the simultaneously enhanced Voc of 0.907 V, Jsc of 26.59 mA cm-2 , and FF of 78.86% contribute to a champion PCE of 19.02%. Therefore, introducing BN bonds into benchmark polymers is a possible avenue toward higher-performance of OSCs.
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The vinylene-bridged helical PDI dimer (PDI2) has been an alternative PDI building block for non-fullerene acceptor (NFAs). However, the development of PDI2 derivatives still lag behind, and most of PDI2 derivatives based organic solar cells (OSCs) only achieved a moderate power conversion efficiencies (PCE) of less than 8%. In this contribution, an acceptor-donor-acceptor-donor-acceptor (A-D-A'-D-A) architecture was introduced to facilitate the improvement of photovoltaic properties. Two acceptors named diIDTIC-PDI2 and diFIDTIC-PDI2 were designed and synthesized, in which a PDI2 moiety flanked with two indacenodithiophene (IDT) units was employed as the D-A'-D core and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC) or fluorinated IC (IC2F) acted as terminal groups, respectively. The photovoltaic performances of these two acceptors were explored using PM1 as the electron donor. Compared to diIDTIC-PDI2, the fluorinated diFIDTIC-PDI2 based OSCs obtained enhanced photovoltaic performance with the best PCE of 9.77%, a VOC of 0.957â V, JSC of 13.58â mA cm-2 and FF of 75.1%. These results illustrate that engineering terminal groups is a robust strategy of enhancing the efficiency of PDI based acceptors with A-D-A'-D-A architecture.
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Preparation of regioisomerically pure 1,6-disubstituted perylene diimide (PDI) is not a trivial task owing to the lack of facile synthetic and separation methodologies for the precursors. Herein, we present a simple synthesis for 1,6-ditriflato-PDI (1,6-diOTf-PDI) using 1,6,9,10-tetrabromo-perylene monoimide 1 as the starting material. The selective methoxylation of 1 at the 1,6-position is the key step. Based on a four-step sequence of selective methoxylation, domino carbonylative amidation, demethylation, and triflation, 1,6-diOTf-PDI can be obtained in a satisfactory yield. Moreover, as a building block, 1,6-diOTf-PDIa can readily undergo Suzuki and Sonogashira cross-coupling reactions.
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Organic electronic-based gas sensors hold great potential for portable healthcare- and environment-monitoring applications. It has recently been shown that introducing a porous structure into an organic semiconductor (OSC) film is an efficient way to improve the gas-sensing performance because it facilitates the interaction between the gaseous analyte and the active layer. Although several methods have been used to generate porous structures, the development of a robust approach that can facilely engineer the porous OSC film with a uniform pore pattern remains a challenge. Here, we demonstrate a robust approach to fabricate porous OSC films by using a femtosecond laser-processed porous dielectric layer template. With this laser-assisted strategy, various polymeric OSC layers with controllable pore size and well-defined pore patterns were achieved. The consequent porous p-type polymer-based device exhibits enhanced sensitivity to the ammonia analyte in the range from 100 ppb to 10 ppm with remarkable reproducibility and selectivity. The micropattern of the active layer was precisely controlled by generating various pore densities in the predecorated templates, which results in modulated ammonia sensitivities ranging from 30 to 65% ppm-1. Furthermore, we show that this approach can be used to fabricate flexible gas sensors with enhanced sensing performance and mechanical durability, which indicate that this femtosecond laser-assisted approach is very promising for the fabrication of next-generation wearable electronics.