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The exploration of mechanical motion in molecular crystals under external stimuli is of great interest because of its potential applications in diverse fields, such as electronics, actuation, or sensing. Understanding the underlying processes, including phase transitions and structural changes, is crucial for exploiting the dynamic nature of these crystals. Here, we present a novel organic compound, PT-BTD , consisting of five interconnected aromatic units and two peripheral alkyl chains, which forms crystals that undergo a drastic anisotropic expansion (33% in the length of one of its dimensions) upon thermal stimulation, resulting in a pronounced deformation of their crystal shape. Remarkably, the transformation occurs while maintaining the single-crystal nature, which has allowed us to follow the crystal-to-crystal transformation by single-crystal analysis of the initial and expanded polymorphs, providing valuable insights into the underlying mechanisms of this unique thermosalient behavior. At the molecular level, this transformation is associated with subtle, coordinated conformational changes, including slight rotations of the five interconnected aromatic units in its structure and increased dynamism in one of its peripheral alkyl chains as the temperature rises, leading to the displacement of the molecules. In situ polarized optical microscopy reveals that this transformation occurs as a rapidly advancing front, indicative of a martensitic phase transition. The results of this study highlight the crucial role of a soft and flexible structural configuration combined with a highly compact but loosely bound supramolecular structure in the design of thermoelastic materials.

Self-assembled polymer vesicles have emerged as exciting and promising materials for their potential application in drug delivery, but the dynamics of stimuli-responsive polymers in these areas with pendant functionality in order to understand the structure-property relationship under different physicochemical conditions is still open to discussion. In this work, nitroxide radical-containing copolymers were synthesized and utilized to investigate local dynamics in their vesicular assemblies. Herein, electron paramagnetic resonance (EPR) spectroscopy was applied to reveal the smart supramolecular vesicular structure and polymer chain dynamics in stimuli-responsive controlled assemblies by considering molecular-level interactions. These interactions and dynamics were dependent on the microenvironment of the assemblies, which might be affected by physicochemical parameters such as radical concentration, pH, redox agent, polarity, and viscosity. These observations help to accomplish quantitative insights into the stimuli-responsive colloidal vesicular assemblies. The vesicles were used as an anticancer drug carrier, which showed high drug loading efficiency (63.65%). The reduction-responsive prompt disassembly accelerated the release. Furthermore, the biocompatibility and anticancer activity were examined by cellular experiments against normal fibroblasts (L929) and human cervical cancer (HeLa) cell lines, respectively. The results demonstrate that this effort provides an easy strategy for designing controllable stimuli-responsive polymer nanosystems which promotes their promising application in cancer treatment.

Polythiophenes, built on the electron-rich thiophene unit, typically possess high-lying energy levels of the lowest unoccupied molecular orbitals (LUMOs) and show hole-transporting properties. In this study, we develop a series of n-type polythiophenes, P1-P3, based on head-to-head-linked 3,3'-dialkoxy-4,4'-dicyano-2,2'-bithiophene (BTCNOR) with distinct side chains. The BTCNOR unit shows not only highly planar backbone conformation enabled by the intramolecular noncovalent sulfur-oxygen interaction but also significantly suppressed LUMO level attributed to the cyano-substitution. Hence, all BTCNOR-based polymer semiconductors exhibit low-lying LUMO levels, which are ∼1.0 eV lower than that of regioregular poly(3-hexylthiophene) (rr-P3HT), a benchmark p-type polymer semiconductor. Consequently, all of the three polymers can enable unipolar n-type transport characteristics in organic thin-film transistors (OTFTs) with low off-currents ( I off s) of 10 -10 -10 -11 A and large current on/off ratios ( I on / I off s) at the level of 10 6 . Among them, polymer P2 with a 2-ethylhexyl side chain offers the highest film ordering, leading to the best device performance with an excellent electron mobility (μ e ) of 0.31 cm 2 V -1 s -1 in off-center spin-cast OTFTs. To the best of our knowledge, this is the first report of n-type polythiophenes with electron mobility comparable to the hole mobility of the benchmark p-type rr-P3HT and approaching the electron mobility of the most-studied n-type polymer, poly(naphthalene diimide- alt-bithiophene) (i.e., N2200). The change of charge carrier polarity from p-type (rr-P3HT) to n-type (P2) with comparable mobility demonstrates the obvious effectiveness of our structural modification. Adoption of n-hexadecyl (P1) and 2-butyloctyl (P3) side chains leads to reduced film ordering and results in 1-2 orders of magnitude lower μ e s, showing the critical role of side chains in optimizing device performance. This study demonstrates the unique structural features of head-to-head linkage containing BTCNOR for constructing high-performance n-type polymers, i.e., the alkoxy chain for backbone conformation locking and providing polymer solubility as well as the strong electron-withdrawing cyano group for lowering LUMO levels and enabling n-type performance. The design strategy of BTCNOR-based polymers provides useful guidelines for developing n-type polythiophenes.

We present here a series of wide-band-gap ( E g : >1.8 eV) polymer donors by incorporating thiophene-flanked phenylene as an electron-donating unit and quinoxaline as an electron-accepting co-unit to attain large open-circuit voltages ( V oc s) and short-circuit currents ( J sc s) in nonfullerene organic solar cells (OSCs). Fluorination was utilized to fine-tailor the energetics of polymer frontier molecular orbitals (FMOs) by replacing a variable number of H atoms on the phenylene moiety with F. It was found that fluorination can effectively modulate the polymer backbone planarity through intramolecular noncovalent S···F and/or H···F interactions. Polymers (P2-P4) show an improved molecular packing with a favorable face-on orientation compared to their nonfluorinated analogue (P1), which is critical to charge carrier transport and collection. When mixed with IDIC, a nonfullerene acceptor, P3 with two F atoms, achieves a remarkable V oc of 1.00 V and a large J sc of 15.99 mA/cm 2 , simultaneously, yielding a power-conversion efficiency (PCE) of 9.7%. Notably, the 1.00 V V oc is among the largest values in the IDIC-based OSCs, leading to a small energy loss ( E loss : 0.62 eV) while maintaining a large PCE. The P3:IDIC blend shows an efficient exciton dissociation through hole transfer even under a small energy offset of 0.16 eV. Further fluorination leads to the polymer P4 with increased chain-twisting and mismatched FMO levels with IDIC, showing the lowest PCE of 2.93%. The results demonstrate that quinoxaline-based copolymers are promising donors for efficient OSCs and the fluorination needs to be fine-adjusted to optimize the interchain packing and physicochemical properties of polymers. Additionally, the structure-property correlations from this work provide useful insights for developing wide-band-gap polymers with low-lying highest occupied molecular orbitals to minimize E loss and maximize V oc in nonfullerene OSCs for efficient power conversion.

Development of high-performance unipolar n-type organic semiconductors still remains as a great challenge. In this work, all-acceptor bithiophene imide-based ladder-type small molecules BTI n and semiladder-type homopolymers PBTI n ( n = 1-5) were synthesized, and their structure-property correlations were studied in depth. It was found that Pd-catalyzed Stille coupling is superior to Ni-mediated Yamamoto coupling to produce polymers with higher molecular weight and improved polymer quality, thus leading to greatly increased electron mobility (μ e ). Due to their all-acceptor backbone, these polymers all exhibit unipolar n-type transport in organic thin-film transistors, accompanied by low off-currents (10 -10 -10 -9 A), large on/off current ratios (10 6 ), and small threshold voltages (∼15-25 V). The highest μ e , up to 3.71 cm 2 V -1 s -1 , is attained from PBTI1 with the shortest monomer unit. As the monomer size is extended, the μ e drops by 2 orders to 0.014 cm 2 V -1 s -1 for PBTI5. This monotonic decrease of μ e was also observed in their homologous BTI n small molecules. This trend of mobility decrease is in good agreement with the evolvement of disordered phases within the film, as revealed by Raman spectroscopy and X-ray diffraction measurements. The extension of the ladder-type building blocks appears to have a large impact on the motion freedom of the building blocks and the polymer chains during film formation, thus negatively affecting film morphology and charge carrier mobility. The result indicates that synthesizing building blocks with more extended ladder-type backbone does not necessarily lead to improved mobilities. This study marks a significant advance in the performance of all-acceptor-type polymers as unipolar electron transporting materials and provides useful guidelines for further development of (semi)ladder-type molecular and polymeric semiconductors for applications in organic electronics.

This study shows that the backbone conformation of head-to-head type 3,3'-dialkyl-2,2'-bithiophene can be tuned via fluorination of the neighboring benzothiadiazole (BTz). Without fluorination, the polymer backbone is highly twisted, whereas difluorination of BTz produced a coplanar backbone. Monofluorination of BTz yielded a tunable polymer backbone conformation depending on the film annealing temperature. In organic thin-film transistors, the polymer with the head-to-head linkages showed a remarkable hole mobility of >0.5 cm 2 V -1 s -1 upon attaining a planar backbone. Thus, the head-to-head linkage does not necessarily lead to backbone nonplanarity, and achieving planar conformation of 3,3'-dialkyl-2,2'-bithiophene has profound implications in materials design for organic semiconducting devices, yielding good solubility, reduced materials synthetic steps, and improved opto-electrical properties.

A face-on oriented and p-doped semicrystalline conjugated polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]-thiadiazole)] (PPDT2FBT), was studied as a hole-transport layer (HTL) in methylammonium lead triiodide-based perovskite solar cells (PVSCs). PPDT2FBT exhibits a mid-band gap (1.7 eV), high vertical hole mobility (7.3 × 10 -3 cm 2 /V·s), and well-aligned frontier energy levels with a perovskite layer for efficient charge transfer/transport, showing a maximum power conversion efficiency (PCE) of 16.8%. Upon doping the PPDT2FBT HTL with a nonhygroscopic Lewis acid, tris(pentafluorophenyl)borane (BCF, 2-6 wt %), the vertical conductivity was improved by a factor of approximately 2, and the resulting PCE was further improved up to 17.7%, which is higher than that of standard PVSCs with 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) as an HTL. After BCF doping, the clearly enhanced carrier diffusion coefficient, diffusion length, and lifetime were measured using intensity-modulated photocurrent and photovoltage spectroscopy. Furthermore, compared to the standard PVSCs with spiro-OMeTAD, the temporal device stability was remarkably improved, preserving the ∼60% of the original PCE for 500 h without encapsulation under light-soaking condition (1 sun AM 1.5G) at 85 °C and 85% humidity, which is mainly due to the highly crystalline conjugated backbone of PPDT2FBT and nonhygroscopic nature of BCF. In addition, formamidinium lead iodide/bromide (FAPbI 3-x Br x )-based PVSCs with the BCF-doped PPDT2FBT as an HTL was also prepared to show 18.8% PCE, suggesting a wide applicability of PPDT2FBT HTL for different types of PVSCs.

A series of polymer semiconductors incorporating 2,1,3-benzothiadiazole-5,6-dicarboxylicimide (BTZI) as strong electron-withdrawing unit and an alkoxy-functionalized head-to-head linkage containing bithiophene or bithiazole as highly electron-rich co-unit are designed and synthesized. Because of the strong intramolecular charge transfer characteristics, all three polymers BTZI-TRTOR (P1), BTZI-BTOR (P2), and BTZI-BTzOR (P3) exhibit narrow bandgaps of 1.13, 1.05, and 0.92 eV, respectively, resulting in a very broad absorption ranging from 350 to 1400 nm. The highly electron-deficient 2,1,3-benzothiadiazole-5,6-dicarboxylicimide and alkoxy-functionalized bithiophene (or thiazole) lead to polymers with low-lying lowest unoccupied molecular orbitals (-3.96 to -4.28 eV) and high-lying highest occupied molecular orbitals (-5.01 to -5.20 eV). Hence, P1 and P3 show substantial and balanced ambipolar transport with electron mobilities/hole mobilities of up to 0.86/0.51 and 0.95/0.50 cm 2 V -1 s -1 , respectively, and polymer P2 containing the strongest donor unit exhibited unipolar p-type performance with an average hole mobility of 0.40 cm 2 V -1 s -1 in top-gate/bottom-contact thin-film transistors with gold as the source and drain electrodes. When incorporated into bulk heterojunction polymer solar cells, the narrow bandgap (1.13 eV) polymer P1 shows an encouraging power conversion efficiency of 4.15% with a relatively large open-circuit voltage of 0.69 V, which corresponds to a remarkably small energy loss of 0.44 eV. The power conversion efficiency of P1 is among the highest reported to date with such a small energy loss in polymer:fullerene solar cells.

New small molecules having modified acceptor strength and π-conjugation length and containing dicyanovinylene (DCV) and tricyanovinylene (TCV) as a strongly electron-accepting unit with indacenodithiophene, IDT(DCV) 2 , IDT(TCV) 2 , and IDTT(TCV) 2 , were synthesized and studied in terms of their applicability to polymer solar cells with PTB7-Th as an electron-donating polymer. Intriguingly, the blended films containing IDT(TCV) 2 and IDTT(TCV) 2 exhibited superior shelf life stabilities of more than 1000 h without any reduction in the initial power conversion efficiency. The low-lying lowest unoccupied molecular orbital energy levels and robust internal morphologies of small TCV-containing molecules could afford excellent shelf life stability.

The molecular weight of a conjugated polymer is one of the key factors determining the electrical, morphological, and mechanical properties as well as its solubility in organic solvents and miscibility with other polymers. In this study, a series of semicrystalline poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT) polymers with different number-average molecular weights (M(n)'s) (PPDT2FBT(L), M(n) = 12 kg/mol; PPDT2FBT(M), M(n) = 24 kg/mol; PPDT2FBT(H), M(n) = 40 kg/mol) were synthesized, and their photovoltaic properties as electron donors for all-polymer solar cells (all-PSCs) with poly[[N,N'-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)] (P(NDI2OD-T2)) acceptor were studied. The M(n) effect of PPDT2FBT on the structural, morphological, electrical, and photovoltaic properties was systematically investigated. In particular, tuning the M(n) induced dramatic effects on the aggregation behaviors of the polymers and their bulk heterojunction morphology of all-PSCs, which was thoroughly examined by grazing incident X-ray scattering, resonant soft X-ray scattering, and other microscopy measurements. High M(n) PPDT2FBT(H) promoted a strong "face-on" geometry in the blend film, suppressed the formation of an excessively large crystalline domain, and facilitated molecularly intermixed phases with P(NDI2OD-T2). Therefore, the optimized all-PSCs based on PPDT2FBT(H)/P(NDI2OD-T2) showed substantially higher hole and electron mobilities than those of PPDT2FBT(L)/P(NDI2OD-T2), leading to a power conversion efficiency exceeding 5%, which is one of the highest values for all-PSCs reported thus far.

The gas-phase reaction of halon 1211 (CBrClF2) with hydrogen has been studied experimentally at atmospheric pressure in a plug flow, isothermal reactor over the temperature range of 673 to 973 K, at residence times ranging from 0.5 to 2.5 s with an input ratio of N2:H2:halon 1211 of 19:10:1. The major carbon containing products include CHClF2, CHBrF2, CH2F2, and CH4. Gas-phase reactions of CHClF2, CCl2F2, and CH2F2 with hydrogen are also investigated under the conditions similar to those for halon 1211 hydrodehalogenation, and the results are used to assist in understanding the mechanism of the reaction of halon 1211 with hydrogen. A kinetic reaction scheme involving 90 species and 430 reaction steps is developed and used to model the halon 1211 hydrodehalogenation reaction. Generally, satisfactory agreement between experimental and computational results is obtained for the production of major species. Using the software package AURORA, the reaction pathways leading to the formation of major products are elucidated. It has been found that the reaction steps involving CF2 are responsible for the formation of CH4.