Energy differences as descriptors for the correlation between JSC and VOC in nonfullerene organic photovoltaics.

ITIC-series nonfullerene organic photovoltaics (NF OPVs) have realized the simultaneous increases of the short-circuit current density (JSC) and open-circuit voltage (VOC), called the positive correlation between JSC and VOC, which could improve the power conversion efficiency (PCE). However, it is complicated to predict the formation of positive correlation in devices through simple calculations of single molecules due to their dimensional differences. Here, a series of symmetrical NF acceptors blended with the PBDB-T donor were chosen to establish an association framework between the molecular modification strategy and positive correlation. It can be found that the positive correlation is modification site-dependent following the energy variation at the different levels. Furthermore, to illustrate a positive correlation, the energy gap differences (ΔEg) and the energy level differences of the lowest unoccupied molecular orbitals (ΔELUMO) between the two changed acceptors were proposed as two molecular descriptors. Combined with the machine learning model, the accuracy of the proposed descriptor is more than 70% for predicting the correlation, which verifies the reliability of the prediction model. This work establishes the relative relationship between two molecular descriptors with different molecular modification sites and realizes the prediction of the trend of efficiency. Therefore, future research should focus on the simultaneous enhancement of photovoltaic parameters for high-performance NF OPVs.

The effect of heavy atoms replacement sites on the luminescent ways of D-A-D type diphenyl sulfone molecules: Thermally activated delayed fluorescence and phosphorescence.

To obtain efficient pure organic thermally activated delayed fluorescence (TADF) materials, introducing non-metal heavy atoms is the common molecular design strategy, enhancing the intrinsically weak spin-orbit coupling (SOC) between singlet and triplet excited states by heavy-atom effect. However, the effect of heavy atom replacement sites is rarely explored. Herein, two series of molecules are investigated on the basis of different heavy atoms replacement sites to reveal the inherent structure-property relationships. The results show that DMSeC-DPS, which O is replaced with Se in periphery of donor units, could exhibit enhanced TADF performance. Because (i) sufficiently small singlet-triplet states energy gap (ΔEST) and enhanced SOC as well as mixed CT/LE character in T1 state could facilitate reverse intersystem crossing process, and (ii) non-radiative consumption are decreased for S1→S0 transition. Additionally, replacement of As at the connection site between donor and acceptor units folds evidently the geometry, leading to much larger ΔEST and enhanced exponentially SOC between T1 and S0 state due to the great participation of heavy atoms of the frontier molecules orbitals and heavy-atom effect. The pure LE character leads to relative stability and slight non-radiative consumption in T1 state. The luminescent way of DMOC-As-DPS would be transformed to phosphorescence. This work provides updated theoretical perspective for the effect of heavy atoms replacement sites and proposes a design strategy for the utilization of non-metal heavy atoms in efficiency organic lighting emitting diodes.

White Emissions Containing Room Temperature Phosphorescence from Different Excited States of a D-π-A Molecule Depending on the Aggregate States.

Development of pure organic molecular materials with room temperature phosphorescence (RTP) and their applications for white emitters have received significant attentions recently. Herein, a D-π-A molecule (DMACPPY) which can realize white emitting under ambient conditions both in the crystal state and the doped-film state by combining RTP with two fluorescent emissions is reported. The white emission from the crystalline sample of DMACPPY consists fluorescence from S2 (the second excited singlet state) and S1 (the first excited singlet state) along with RTP from T1 (the first excited triplet state), namely, SST-type white light. While, the white emission from the poly methyl methacrylate (PMMA) film doped with DMACPPY contains fluorescences from S2 and S1 , and RTP from T2 (the second excited triplet state) rather than T1 (STS type). DMACPPY cannot exhibit white spectrum within alternative crystalline state since inferior RTP intensity despite similar ternary emissions. The results demonstrate that the emissive properties for excited states of DMACPPY can be tuned by changing the aggregate state from crystalline to dispersion state in PMMA film. This new RTP emitter fulfills the talent for white emitting and achieves dual-mode white emissions, invisibly, expands the application range for pure organic and heavy atom-free RTP materials.

Revealing the reason for the reversal of properties from fullerene to nonfullerene.

The existence of an inflection point between fullerene and nonfullerene molecules was demonstrated using bowl-nonfullerene models, which were proposed to explore the key points relating to the different properties. This study explains the differences in the stacking configurations of the inflection points and reveals the reason for the inversion of properties, which is caused by small structural differences.

Charge Transfer Mechanisms Regulated by the Third Component in Ternary Organic Solar Cells.

For ternary organic solar cells (T-OSCs), introducing the third component (D2) can significantly enhance the efficiency of cell while still maintaining easy fabrication. However, it brings difficulty in physical understanding of the fundamental mechanism because of the more complicated photophysical processes in T-OSCs. Accordingly, how the guest donor D2 regulates the charge transfer mechanism was explored in theory using three T-OSCs containing two donors and an acceptor. The results point out that larger differences in molecular weight and/or backbone between D2 and the host donor D1 cause different charge transfer mechanisms, which hardly provide a coexisting charge transfer path. Besides, strong absorption capacity of D2 with a high oscillator strength would produce favorable regulation of the charge transfer mechanism. Therefore, this work clarifies the influence of D2 on the charge transfer mechanism in T-OSCs, which suggests that the method of improving the power conversion efficiency cannot be generalized but rather must be tailored to specific conditions.

The mechanism of the selective binding ability between opiate metabolites and acyclic cucurbit[4]uril: an MD/DFT study.

Subtle changes in molecular structure often lead to significant differences in host-guest interactions, which result in different host-guest recognition capabilities and dynamics behaviours in complex formation. Herein, we reveal the influence of the guest substituents on host-guest molecular recognition by molecular dynamics (MD) simulation and density functional theory (DFT) approaches. The results suggest that the binding energy barrier of acyclic cucurbit[4]uril (ACB[4]) with opiate metabolites gradually decreases. The methyl group in morphine (MOR) and morphine-3-glucuronide (M3G) strengthens the hydrophobicity of the guest, while depressing the energy loss of the desolvation of polar groups (e.g. hydroxyl) inside the ACB[4] cavity. However, in M3G, the 3-glucuronide group located outside the ACB[4] host cavity effectively alleviates the unfavourable desolvation effect of the hydroxyl and increases the binding constant by two orders of magnitude (compared with normorphine (NMOR)). Our findings stressed the essentiality of the binding mode and intermolecular noncovalent interactions in the host-guest selective binding ability.

Design of single-porphyrin donors toward high open-circuit voltage for organic solar cells via an energy level gradient-distribution screening strategy of fragments: a theoretical study.

Open-circuit voltage (VOC) is a key factor for improving the power conversion efficiency (PCE) of bulk heterojunction (BHJ) organic solar cells (OSCs). At present, increasing attention has been devoted towards modifying π bridges in single-porphyrin small molecule donors with an A-π-D-π-A configuration to reduce the highest occupied molecular orbital (HOMO) levels and improve the VOC of devices. However, how to screen the π bridges is a key issue. In this work, nine π bridges were screened by the HOMO level gradient-distribution strategy of fragments (electron-donating donor (D), π bridges, and electron-withdrawing acceptor (A)), where fragments meeting the requirements were combined into five novel small molecule donors. Meanwhile, in order to test whether the strategy is beneficial to increasing VOC, [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) was selected as the acceptor material. The energy levels of all molecules were compared and the photoelectric properties (i.e., energy gap, energy driving force, reorganization energy, intermolecular charge transfer rate, charge recombination rate, and VOC) of the five small molecules were studied. The results showed that the HOMO levels of porphyrin donors could be significantly lowered via this strategy, and VOC was raised without losing the short-circuit current (JSC) and fill factor (FF) of the devices. Meanwhile, the designed five small molecules could be used as donor candidates to improve the performance of OSCs.

Star-Shaped Non-Fullerene Small Acceptors for Organic Solar Cells.

Over the past decade, organic solar cells (OSCs) have received considerable attention from the scientific community and are considered one of the most important sources of low-cost electricity production. Recently, OSC-based on star-shaped small-molecule (SM) non-fullerene acceptors (NFAs) have developed rapidly, and the highest power conversion efficiency (PCE) has exceeded 10 %. The star-shaped SM NFAs not only have three-dimensional charge-transport characteristics similar to fullerenes but also have a strong light absorption capacities and easily tunable energy levels. They are potential candidates as outstanding acceptor materials. In this Review, research progress in of star-shaped SM NFAs OSCs is reviewed specifically. Moreover, the influence of molecular structure, central unit, and peripheral linking group on OSC performance has been evaluated systematically. This Review could stimulate inspiration for designing high-performance OSC acceptor materials in the future.

Construction of Various Supramolecular Assemblies from Rod-Coil Molecules Containing Biphenyl and Anthracene Groups Driven by Donor-Acceptor Interactions.

Rod-coil amphiphilic functional molecules, comprising a rigid aromatic building block and hydrophilic oligoether dendrons as the coil segments, were synthesized. These compounds exhibit a powerful self-organizing ability to form supramolecular nanoparticles and long nanofibers in tetrahydrofuran/water solution, by controlling the intermolecular interaction of the rigid blocks. These molecules are able to form supramolecular polymers and, subsequently, to form sheetlike nanoaggregates, through charge-transfer interactions by the addition of a guest molecule, tetracyanoquinodimethane. Notably, upon addition of water-soluble 2,4,6-trinitrophenol, the self-assembly of these molecules exhibits the antagonistic effect owing to donor-acceptor and hydrophobic-hydrophilic interactions among the molecules. The experimental results reveal that various morphologies of rod-coil molecular assemblies can be obtained by tuning the molecular interaction and the hydrophilicity of guest electron-acceptor molecules. Interestingly, the cross-coupling reaction between phenylboronic acid and chlorobenzene occurs within the charge complexes of these molecular aggregates. This occurs in the nanoenvironment that affords an extremely concentrated reaction zone and reduces the activation energy barrier required for the cross-coupling reaction.

From blue to full color - theoretical design and characterization of a series of Ir(iii) complexes containing azoline ligand with potential application in OLEDs.

Two reported Ir(iii) complexes 1a and 1b containing oxazoline and imidazoline in ancillary ligand, respectively, were investigated by DFT/TD-DFT method. In order to obtain full-color display materials, we designed a group of Ir(iii) complexes 2a-3d based on 1a, which exhibits higher quantum efficiency in phosphorescence, by introducing electron-donating/electron-withdrawing moieties to different positions of the ancillary ligand to adjust emission color. In addition to calculating the radiation rate and analyzing its determining factors, we also estimated nonradiative ability by evaluating the spin-orbit coupling matrix element between the ground state (S0) and the lowest triplet state (T1) as well as the reorganization energy from T1 to S0 to estimate quantum efficiency more accurately. In particular, an in-depth analysis on the contribution of each vibration mode to reorganization energy helped us to identify the effect of substituents on the nonradiative process. Besides, charge injection/transfer properties and energy relation of the states related to exciton quenching via the triplet metal-centered state were also examined, which provide an estimation on the OLED performance of our designed complexes. Overall, we expect 2b and 3c to be more efficient blue-emitting emitters than 1a and 3a and 3b to be efficient green and red emitters, respectively.

Theoretical study on the charge transfer mechanism at donor/acceptor interface: Why TTF/TCNQ is inadaptable to photovoltaics?

A combined molecular dynamics (MD) and quantum chemical (QC) simulation method is utilized to investigate charge generation mechanism at TTF/TCNQ (tetrathiafulvalene/tetracyanoquinodimethane) heterojunction, which is a controversial donor/acceptor (D/A) interface for organic photovoltaic (OPV) devices. The TTF/TCNQ complexes extracted from MD simulation are classified into parallel and herringbone packings. And then, the amounts of charge transferred from ground states to different excited states and the corresponding energies of charge transfer (CT) state are compared and analyzed using QC simulation. Moreover, the electron transfer/recombination rates for these interfacial configurations are also studied. From these data, we have elucidated the underlying reason why TTF/TCNQ heterojunction is inadaptable to OPV application. One main reason is that large |ΔGCT| (the absolute value of Gibbs free energy change of CT) forms a large energy barrier, limiting exciton dissociation at the TTF/TCNQ heterojunction, and small |ΔGCR| (the absolute value of Gibbs free energy change of charge recombination) performs the easy recombination to the ground state.