Appending Coronene Diimide with Carbon Nanohoops Allows for Rapid Intersystem Crossing in Neat Film.

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 4.5 ns and 238 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.

Veil of the Charge Transfer State in Bay-Annulated Indigo-Based Donor-Acceptor Systems: Charge Separation versus Singlet Fission.

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.

Quantum interference effects elucidate triplet-pair formation dynamics in intramolecular singlet-fission molecules.

Quantum interference (QI)-the constructive or destructive interference of conduction pathways through molecular orbitals-plays a fundamental role in enhancing or suppressing charge and spin transport in organic molecular electronics. Graphical models were developed to predict constructive versus destructive interference in polyaromatic hydrocarbons and have successfully estimated the large conductivity differences observed in single-molecule transport measurements. A major challenge lies in extending these models to excitonic (photoexcited) processes, which typically involve distinct orbitals with different symmetries. Here we investigate how QI models can be applied as bridging moieties in intramolecular singlet-fission compounds to predict relative rates of triplet pair formation. In a series of bridged intramolecular singlet-fission dimers, we found that destructive QI always leads to a slower triplet pair formation across different bridge lengths and geometries. A combined experimental and theoretical approach reveals the critical considerations of bridge topology and frontier molecular orbital energies in applying QI conductance principles to predict rates of multiexciton generation.

Femtosecond Laser-Assisted Device Engineering: Toward Organic Field-Effect Transistor-Based High-Performance Gas Sensors.

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.

Achieving Symmetry-Breaking Charge Separation in Perylenediimide Trimers: The Effect of Bridge Resonance.

Symmetry-breaking charge separation (SB-CS) provides a very promising option to engineer a novel light conversion scheme, while it is still a challenge to realize SB-CS in a nonpolar environment. The strength of electronic coupling plays a crucial role in determining the exciton dynamics of organic semiconductors. Herein, we describe how to mediate interchromophore coupling to achieve SB-CS in a nonpolar solvent by the use of two perylenediimide (PDI)-based trimers, 1,7-tri-PDI and 1,6-tri-PDI. Although functionalization at the N-atom decreases electronic coupling between PDI units, our strategy takes advantage of "bridge resonance", in which the frontier orbital energies are nearly degenerate with those of the covalently linked PDI units, leading to enhanced interchromophore electronic coupling. Tunable electronic coupling was realized by the judicious combination of "bridge resonance" with N-functionalization. The enhanced mixing between the S1 state and CT/CS states results in direct observation of the CT band in the steady-state UV-vis absorption and negative free energy of charge separation (ΔGCS) in both chloroform and toluene for the two trimers. Using transient absorption spectroscopy, we demonstrated that photoinduced SB-CS in a nonpolar solvent is feasible. This work highlights that the use of "bridge resonance" is an effective way to control exciton dynamics of organic semiconductors.

Molecular Regulation on Carbonyl-Based Organic Cathodes: Toward High-Rate and Long-Lifespan Potassium-Organic Batteries.

Organic redox-active molecules have been identified as promising cathodes for practical usage of potassium-ion batteries (PIBs) but still struggle with serious dissolution problems and sluggish kinetic properties. Herein, we propose a pseudocapacitance-dominated novel insoluble carbonyl-based cathode, [2,6-di[1-(perylene-3,4,9,10-tetracarboxydiimide)]anthraquinone, AQ-diPTCDI], which possesses high reversible capacities of 150 mAh g-1, excellent cycle stability with capacity retention of 88% over 2000 cycles, and fast kinetic properties. The strong intermolecular interactions of AQ-diPTCDI and in situ formed cathode electrolyte interphase films support it against the dissolution problem. The high capacitive-like contribution in capacities and fast potassium-ion diffusion enhance its reaction kinetics. Moreover, a symmetric organic potassium-ion battery (OPIB) based on AQ-diPTCDI electrodes also exhibits outstanding K-storage capability. These results suggest that AQ-diPTCDI is a promising organic cathode for OPIBs and provide a practicable route to realize high-performance K storage.

π-Extension, Selenium Incorporation, and Trimerization: "Three in One" for Efficient Perylene Diimide Oligomer-Based Organic Solar Cells.

Perylene diimide (PDI) and the vinylene-bridged helical PDI oligomers are versatile building blocks for constructing nonfullerene acceptors (NFAs). In this contribution, a benzene-cored star-shaped NFA, namely, TPDI2-Se, was designed and synthesized for organic solar cells (OSCs). The NFA with smaller π-conjugated blades, namely, TPDI-Se, was synthesized for comparison. Using the commercially available PTB7-Th as the electron donor, the best power conversion efficiency (PCE) of 3.62% was obtained for TPDI-Se-based OSCs. However, a much higher PCE of 8.59% was achieved for TPDI2-Se-based devices owing to the π-extension in the peripheral panels. Moreover, the photovoltaic performance of TPDI2-Se-based OSCs is also superior to those of the parent NFA TPDI2 (PCE of 7.84%)- and the blade moiety PDI2-Se (PCE of 6.61%)- based ones. Additionally, a remarkable short-circuit current (Jsc) value of 17.21 mA/cm2 was obtained for TPDI2-Se-based OSCs, which is among the highest Jsc values reported in PDI-based OSCs. These results argue that the so-called "three in one" molecule design strategy of π-extension, selenium incorporation, and trimerization offers a robust approach to constructing high-performance PDI-based NFAs.

Isomeric Effect on Optoelectronic Properties and Photovoltaic Performance of Anthraquinone-Core Perylene Diimide (PDI) and Helical PDI dimers.

Isomerism heavily influences the optoelectronic properties and self-assembly behavior of compounds and subsequently affects their device performance. Herein, two pairs of isomeric perylene diimide (PDI) dimers, PDI and PDI2, were designed and synthesized. The electron-deficient 9,10-anthraquinone group was employed as the bridge, and thus, the resultant dimers exhibited an acceptor-acceptor-acceptor (A-A-A) structure. To determine the isomeric effects on the optoelectronic properties and photovoltaic performance of these dimers, their absorptivity, luminescence, and redox behavior were studied. Bulk heterojunction organic solar cells based on these four dimers were fabricated and measured. The two PDI dimers exhibited clear differences in photovoltaic performance, whereas the two PDI2 analogues showed similar power conversion efficiencies (PCEs). The PCEs of the two PDI2 dimers are much higher than those of the PDI dimers. These results illustrate that the isomeric effect of PDI dimers is much larger than that of PDI2 dimers on the device performance, and proper expansion of conjugation could improve the device performance.