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Summary Developing novel electron-deficient monomers is crucially important for the future development of non-fullerene organic solar cells. Here, we report a new electron-deficient monomer naphthalenothiophene imide (NTI) and NTI-based copolymers PNTB and PNTB-2T. The strong electron-withdrawing ability of NTI could effectively lower the HOMO level of the polymer that facilitates the tuning of the polymer’s physical properties while simultaneously maintaining the low-lying HOMO value. Polymer chains modification by introducing extra thiophenes results in the closed π−π stacking and ordered polymer chain packing of PNTB-2T and is proven to be an effective strategy to increase the device performance. Thus, solar cell devices for PNTB-2T:Y6 exhibit an efficiency of 16.72%, which is further enhanced to 17.35% by the third component PC71BM, whereas that for PNTB:Y6 is only 3.81%. Importantly, PNTB-2T-based devices exhibit excellent batch-to-batch reproducibility. These features make this family of polymer donors very promising and the design strategies will enlighten future development of high-performance polymer donors for organic solar cells (OSC).

High-performance polymer donors are highly demanded to fulfil the potential of layer-by-layer (LBL) processed organic solar cells (OSCs). In this study, we present an effective method to develop high-performance polymer donors for LBL-OSCs by manipulating their solubility properties. The solubility of naphthalenothiophene imide (NTI)-based polymers could be easily manipulated by employing linear or branched alkyl chains in NTI. The polymer PNTB6-Cl with linear alkyl chains insoluble in chloroform could tolerate the chloroform processing by washing away the polymers only in the amorphous region, resulting in an LBL film with a much smoother surface and more efficient photoluminescence quenching, while chloroform-soluble polymer PNTB-Cl did not. PNTB6-Cl:N3 based LBL devices exhibited an efficiency of 17.59%, much higher than 15.24% for PNTB-Cl:N3 based devices and 16.20% for control devices based on PM6:N3. Importantly, the excellent batch-to-batch reproducibility of PNTB6-Cl overcomes the notorious batch-dependent issue in polymer donors, indicating that PNTB6-Cl is a promising polymer donor for LBL-OSCs. Our studies demonstrate that the solubility property of a polymer could significantly impact electron acceptor penetration, phase separation and photovoltaic performance of LBL-OSCs, which provide the guidelines for high-performance polymer donor design.

Previous studies have proposed that the presence of a flexible π-bridge linker is crucial in activating intramolecular singlet exciton fission (iSEF) in multichromophoric systems. In this study, we report the photophysical properties of three analogous perylene diimide (PDI) dendritic tetramers showing flexible/twisted π-bridged structures with α- and β-substitutions and a rigid/planar structure with a β-fused ring (βC) connection to a benzodithiophene-thiophene (BDT-Th) core. The rigidity and enhanced planarity of βC lead to significant intramolecular charge transfer and triplet formation via an intersystem crossing pathway. Steady-state spectroscopic measurements reveal similar absorption and emission spectra for the α-tetramer and the parent PDI monomer. However, their fluorescence quantum yield is significantly different. The negligible fluorescence yield of the α-tetramer (0.04%) is associated with a competitive nonradiative decay pathway. Indeed, for this twisted compound in a high polar environment, a fast and efficient iSEF with a triplet quantum yield of 124% is observed. Our results show that the α-single-bond connections in the α compound are capable of interrupting the coupling among the PDI units, favoring iSEF. We propose that the formation of the double triplet (1[TT]) state is through a superposition of singlet states known as [S1S0][TT]CT, which has been suggested previously for pentacene derivatives. Using steady-state and time-resolved spectroscopic experiments, we demonstrate that the conformational flexibility of the linker itself is necessary but not sufficient to allow iSEF. For the case of the other twisted tetramer, β, the strong π-π co-facial interactions between the adjacent PDI units in its structure lead to excimer formation. These excimer states trap the singlet excitons preventing the formation of the 1[TT] state, thus inhibiting iSEF.

We investigate the effect of molecular geometry and conformational flexibility on electronic coupling and charge transfer interactions within propeller-shaped perylene diimide (PDI) tetramer arrays differing by the number of covalent linkages to a central spirobifluorene core. Electronic spectra of tetramers with one (“floppy”) or two (“rigid”) bay covalent linkages display evidence of charge transfer character in either ground or excited states. Floppy tetramers exhibit marked red-shifted and broadened absorption features that we assign as overlapping inter-PDI charge transfer and PDI-centered π–π* transitions, whereas rigid tetramers retain features similar to single PDI molecules, albeit with broader line widths. Interestingly, both tetramers exhibit charge transfer character in their fluorescence emission, but this is most prominent in the rigid tetramer, which displays dominant long-lived excimer behavior in addition to a minority component resembling single PDI-like emission. We then use single-mole...

The non-fullerene electron acceptor, TPB, exhibits a unique cross-like molecular geometry which helps it to stay preferentially at the interfaces between PTB7-Th and PC71BM, when it is used as the ...

Bi-thieno[3,4]pyrrole-4,6-dione (bi-TPD) based copolymers containing 1,2-bis(2-thienyl)ethene (P1) and 1,2-diphenylethene (P2) units are synthesized and characterized. Their physicochemical and electrical properties as well as molecular packing structures in thin films have been fully investigated. P1 has higher HOMO energy levels and smaller bandgap than P2, which is attributed to the stronger electron-donating ability of 1,2-bis(2-thienyl)ethene unit. Both polymers form continuous films and adopt face-on and edge-on co-orientation in the aggregation states. The crystallinity of P1 film is higher than that of P2 film. The optimal field-effect mobility is 0.74 cm2V−1s−1 for P1 films and 0.32 cm2V−1s−1 for P2 films. These results demonstrated the merits of 1, 2-bis(2-thienyl)ethene unit and the potential applications of bi-TPD based polymers in high performance polymer transistors.

Two types of electron acceptors were synthesized by coupling two kinds of electron-rich cores with four equivalent perylene diimides (PDIs) at the α-position. With fully aromatic cores, TPB and TPSe have π-orbitals spread continuously over the whole aromatic conjugated backbone, unlike TPC and TPSi, which contain isolated PDI units due to the use of a tetrahedron carbon or silicon linker. Density functional theory calculations of the projected density of states showed that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for TPB are localized in separate regions of space. Further, the LUMO of TPB shows a greater contribution from the orbitals belonging to the connective core of the molecules than that of TPC. Overall, the properties of the HOMO and LUMO point at increased intra-molecular delocalization of negative charge carriers for TPB and TPSe than for TPC and TPSi and hence at a more facile intra-molecular charge transfer for the former. The film absorption and emission spectra showed evidences for the inter-molecular electron delocalization in TPB and TPSe, which is consistent with the network structure revealed by X-ray diffraction studies on single crystals of TPB. These features benefit the formation of charge transfer states and/or facilitate charge transport. Thus, higher electron mobility and higher charge dissociation probabilities under J

Gold nanoclusters (AuNCs) have attracted much attention for tumor theranostics in recent years because of their ability of renal clearance and to escape the reticuloendothelial system (RES) sequestration. In this study, we presented a novel method to synthesize 68Ga-doped (labeled) AuNCs by simultaneous reduction of 68GaCl3 and HAuCl4 by glutathione. As synthesized 68Ga-doped, glutathione-coated AuNCs (68Ga-GSH@AuNCs) were ultrasmall in size (

A new series of donor–acceptor ladder-type molecules were synthesized via Scholl reaction. These molecules contain up to 25-fused rings but still show good air stability and good solubility. The ring-fusing reaction is found to be sensitive to the nature of the side-chain in donor units. The molecular conformations were investigated by 2D NMR and DFT calculations. The photophysical properties were investigated and an intense intramolecular charge-transfer was observed. All of the molecules exhibit two-photon absorption (TPA) activity, and their TPA cross-section shows a linear relationship with increasing conjugation length of the thienoacene-PDI derivatives.

This paper describes the synthesis and application of βTPB6 and βTPB6-C as electron acceptors for organic solar cells. Compound βTPB6 contains four covalently bonded PDIs with a BDT-Th core at the β-position. The free rotation of PDIs renders βTPB6 with varying molecular geometries. The cyclization of βTPB6 yields βTPB6-C with high rigidity of the molecular geometry and enlarged conjugated skeleton. The inverted solar cells based on βTPB6-C and PTB7-Th as the donor polymer exhibited the highest efficiency of 7.69% with Voc of 0.92 V, Jsc of 14.9 mAcm–2, and FF of 0.56, which is 31% higher than that for βTPB6 based devices. The larger fraction of βTPB6-C and PTB7-Th than that of βTPB6:PTB7-Th in a blend film takes a face-on orientation packing pattern for π-systems that benefits the charge transport and hence higher PCE value than that for βTPB6:PTB7-Th. It was also found that a proper DIO:DPE additive further enhances this trend, which results in an increase of the PCE value for βTPB6-C:PTB7-Th while decr...

Bithienopyrroledione (bi-TPD) based polymers P1 and P2 are designed and synthesized. Photovoltaic devices based on P1:PC71BM and P2:PC71BM blend films show power conversion efficiencies (PCEs) of 8.22% and 9.08%, respectively, whereas devices based on their thienopyrroledione (TPD)-based analogue P3 and PC71BM blend films display a PCE of 5.10%.

A novel series of amphiphilic TC-PEG molecules were designed and synthesized based on the orthogonal cyclophane unit. These molecules were able to self-assemble from 1D nanofibers and nanobelts to 2D ultrathin nanosheets (3 nm thick) in a controlled way by tuning the length of PEG side-chains. The special structure of the cyclophane moiety allowed control in construction of nanostructures through programmed noncovalent interactions (hydrophobic–hydrophilic interaction and π–π interaction). The self-assembled nanostructures were characterized by combining real space imaging (TEM, SEM, and AFM) and reciprocal space scattering (GIWAXS) techniques. This unique supramolecular system may provide a new strategy for the design of materials with tunable nanomorphology and functionality.

Developing highly efficient photocatalyts for water splitting is one of the grand challenges in solar energy conversion. Here, we report the rational design and synthesis of porous conjugated polymer (PCP) that photocatalytically generates hydrogen from water splitting. The design mimics natural photosynthetics systems with conjugated polymer component to harvest photons and the transition metal part to facilitate catalytic activities. A series of PCPs have been synthesized with different light harvesting chromophores and transition metal binding bipyridyl (bpy) sites. The photocatalytic activity of these bpy-containing PCPs can be greatly enhanced due to the improved light absorption, better wettability, local ordering structure, and the improved charge separation process. The PCP made of strong and fully conjugated donor chromophore DBD (M4) shows the highest hydrogen production rate at ∼33 μmol/h. The results indicate that copolymerization between a strong electron donor and weak electron acceptor into the same polymer chain is a useful strategy for developing efficient photocatalysts. This study also reveals that the residual palladium in the PCP networks plays a key role for the catalytic performance. The hydrogen generation activity of PCP photocatalyst can be further enhanced to 164 μmol/h with an apparent quantum yield of 1.8% at 350 nm by loading 2 wt % of extra platinum cocatalyst.

Perylene diimide (PDI) derivatives functionalized at the ortho-position (αPPID, αPBDT) were synthesized and used as electron acceptors in non-fullerene organic photovoltaic cells. Because of the good planarity and strong π-stacking of ortho-functionalized PDI, the αPPID and αPBDT exhibit a strong tendency to form aggregates, which endow the materials with high electron mobility. The inverted OPVs employing αPDI-based compounds as the acceptors and PBT7-Th as the donor give the highest power conversion efficiency (PCE) values: 4.92% for αPBDT-based devices and 3.61% for αPPID-based devices, which are, respectively, 39% and 4% higher than that of their β-substituted counterparts βPBDT and βPPID. Charge separation studies show more efficient exciton dissociation at interfaces between αPDI-based compounds and PTB7-Th. The results suggest that α-substituted PDI derivatives are more promising electron acceptors for organic photovoltaic (OPV) components than β-isomers.

Bi-thieno[3,4-c]pyrrole-4,6-dione (bi-TPD) and oligothiophene copolymer semiconductors P1–P4, with different alkyl side chain densities and orientations, were synthesized. Their physicochemical properties were systematically characterized. With trimethoxy(octadecyl)silane (OTMS) modified SiO2 as substrates, the as-spun thin films of P1, P3 and P4 adopted the face-on packing structure while the P2 films displayed the edge-on packing arrangement. The packing differences of P1–P4 were ascribed to their different alkyl chain densities and orientations. The higher alkyl chain density is favorable to the face-on packing structure. After thermal annealing, the packing orientation of P2 remained and the packing structures of P1, P3 and P4 changed. P1 and P4 based films exhibited the coexistence of the edge-on and face-on packing structures in which the edge-on structure was predominant, and P3 based thin films were converted to the edge-on packing arrangement. The relationship between the aggregation structures and charge carrier transport properties of these films was explored through thin film transistors. All devices exhibited p-channel behavior with a maximum mobility larger than 1.0 cm2 V−1 s−1. Interestingly, the P3 films with face-on packing structures displayed a high mobility up to 1.18 cm2 V−1 s−1 (average mobility of 1.02 cm2 V−1 s−1), very close to the edge-on packed films which showed a maximum mobility of 1.4 cm2 V−1 s−1 (average mobility of 1.16 cm2 V−1 s−1). These results demonstrated, similar to edge-on packing structures, the face-on packing arrangement with π–π interactions facilitated charge carrier transport.

Self-assembly of monolayers of functional molecules on dielectric surfaces is a promising approach for the development of molecular devices proposed in the 1970s. Substrate chemically bonded self-assembled monolayers of semiconducting conjugated molecules exhibit low mobility. And self-assembled monolayer molecular crystals are difficult to scale up and limited to growth on substrates terminated by hydroxyl groups, which makes it difficult to realize sophisticated device functions, particularly for those relying on n-type electron transport, as electrons suffer severe charge trapping on hydroxyl terminated surfaces. Here we report a gravity-assisted, two-dimensional spatial confinement method for bottom-up growth of high-quality n-type single-crystalline monolayers over large, centimeter-sized areas. We demonstrate that by this method, n-type monolayer molecular crystals with high field-effect mobility of 1.24 cm2 V−1 s−1 and band-like transport characteristics can be grown on hydroxyl-free polymer surface. Furthermore, we used these monolayer molecular crystals to realize high-performance crystalline, gate-/light-tunable lateral organic p–n diodes., New methods for obtaining large-area monolayer molecular crystals (MMCs) on hydrophobic surfaces are needed to realize the full potential of MMCs for organic electronics. Here, the authors demonstrate bottom-up growth of high-grade n-type MMCs, which show superior performance in device applications.

π-Extended nine-ring-fused linear thienoacenes 1a–c with internal thieno[3,2-b;4,5-b′]dithiophene substructures were synthesized. Their optical and electrochemical properties were investigated. Thin-film transistor characteristics showed all compounds displayed high device reproducibility and nearly no dependence on substrate temperatures. The highest performance was observed for 1c-based devices with mobility up to 1.0 cm2/Vs and current on/off ratio of 10(7), whereas the maximum mobility was 0.5 cm2/Vs for 1b and 0.011 cm2/Vs for 1a.

Thieno[3,4-c]pyrrole-4,6-dione (TPD) containing copolymer semiconductors P1–P3 were strategically designed and successfully synthesized. Their physicochemical properties were thoroughly investigated. All polymers exhibited good solution processability and high humidity stability in thin film transistors (TFTs). Transistor electrical characterization showed the device performance was sensitive to the alkyl chain substituent orientations of the polymers. A maximum TFT hole mobility of ∼1.29 cm2/(V s) was observed for P3-based devices, a recorded mobility for TPD containing polymer semiconductors reported to date. The corresponding thin-film morphologies and polymer chains packing were investigated in detail by AFM and 2D-GIXD to correlate with the alkyl orientation-dependent carrier mobility of P1–P3. Experimental results showed the alkyl chain orientations determined the polymer chains packing pattern in the thin films, the film morphologies, and the resulting device performances of P1–P3.

N-Alkyl substituted pyrroloindacenodithiophene (PIDT) and their phenyl substituted derivatives were synthesized. Their single-crystal structures and electrochemical and spectroscopic properties were investigated. Experimental results showed PIDT displayed strong electron-donating properties, reversible redox behaviors, and strong fluorescence and could be controlled to oxidize to radical cation and dication with distinctive optical changes. These attractive properties demonstrated the potential applications of PIDT in the field of switches, molecular machines, and information memories.

A series of dicyanomethylene-substituted 2,5-di(thiophen-2-yl)thieno[3,2-b]thieno-quinoids, in which soluble alkyl chains (2-decyltetradecyls) are substituted at different positions (namely, 2,2′-positions (Compound 1); 3,3′- positions (Compound 2); 6,6′-positions (Compound 3)), are strategically designed and successfully synthesized. The photophysical and electrochemical properties as well as molecular packing of these new compounds are thoroughly investigated. Thin film transistor measurements reveal that Compounds 1–3 display markedly different charge transport performance. The solution processed thin film transistors of Compound 2 exhibits the highest electron mobility of up to 0.22 cm2 V−1 s−1 under ambient conditions, one and three orders of magnitude higher than those of Compounds 3 and 1, respectively, demonstrating the strong impact of alkyl chain orientations on transistor performance.

Developing photocatalytic systems for water splitting to generate oxygen and hydrogen is one of the biggest chemical challenges in solar energy utilization. In this work, we report the first example of heterogeneous photocatalysts for hydrogen evolution based on in-chain cobalt-chelating conjugated polymers. Two conjugated polymers chelated with earth-abundant cobalt ions were synthesized and found to evolve hydrogen photocatalytically from water. These polymers are designed to combine functions of the conjugated backbone as a light-harvesting antenna and electron-transfer conduit with the in-chain bipyridyl-chelated transition metal centers as catalytic active sites. In addition, these polymers are soluble in organic solvents, enabling effective interactions with the substrates as well as detailed characterization. We also found a polymer-dependent optimal cobalt chelating concentration at which the highest photocatalytic hydrogen production (PHP) activity can be achieved.

14,14,15,15-Tetracyano-6,13-pentacenequinodimethane (TCPQ) diimide, a new tetracyanoquinodimethane analogue with extended conjugation and imide substituents, was synthesized by double Diels–Alder reactions and a Knoevenagel condensation reaction. Experimental results showed that TCPQ diimide has a low LUMO energy level (–4.03 eV) and good solubility in organic solvents.

A donor–acceptor–donor (D–A–D) type small molecule DHB-QDTB, with dicyano-substituted quinoidal benzo[1,2-b:4,5-b′]dithiophene as the acceptor, was designed and synthesized. A high electron mobility up to 0.88 cm2 V−1 s−1 was observed for DHB-QDTB based transistors under ambient conditions, suggesting quinoidal benzo[1,2-b:4,5-b′]dithiophene is an excellent acceptor unit in D–A type n-channel organic semiconductors.

OBJECTIVE To discuss the influence of Suoquan capsule (SQJN) on the detrusor of D-galactose mimetic rats, and to explore the mechanism of reducing urine. METHOD Investigate the enzymes (ATPase, SDH, SOD, MDA, Na+ -K+ -ATPase, Ca2+ - Mg2+ -ATPase) which influence the production and excretion of urine and the reactivity of urinary detrusor strips to different concentrations of ISO and ATP. RESULT Compared with the model group, the activity of SOD, Na+ -K+ -ATPase, Ca2+ -Mg2+ -ATPase and SDH increased significantly in aging rats after administrating SQJN (P < 0.01); the complaisance and elasticity of bladder also increased (P < 0.05). The frequency of spontaneous contraction and the MDA decreased significantly (P < 0.05-0.01). The decreased relaxation response to ISO and increased contractile response to ATP were also changed after administrating SQJN. CONCLUSION SQJN can regulate the metabolism of fluid through recovering the normal physiologic function of the detrusor of bladder.

This paper considers the stability analysis problem of nD discrete-time systems. It is shown that the problems of stability test and stability margin computation for an nD system described by Roesser model can be recast into μ analysis problems in a unified way, thus can be solved effectively by using the commercially available software package.