Considerable efforts have been devoted to achieving stable acene derivatives for electronic applications; however, the instability is still a major issue for such derivatives. To achieve higher ...stability with minimum structural change, CC units in the acenes were replaced with isoelectronic BN units to produce a novel BN‐embedded tetrabenzopentacene (BNTBP). BNTBP, with a planar structure, is highly stable to air, moisture, light, and heat. Compared with its carbon analogue tetrabenzopentacene (TBP), BN embedment lowered the highest occupied molecular orbital (HOMO) energy level of BNTBP, changed the orbital distribution, and decreased the HOMO orbital coefficients at the central carbon atoms, which stabilize BNTBP molecules upon exposure to oxygen and sunlight. The single‐crystal microribbons of BNTBP exhibited good performance in field‐effect transistors (FETs). The high stability and good mobility of BNTBP indicates that BN incorporation is an effective approach to afford stable large‐sized acenes with desired properties.
Make stable: BN‐embedment is demonstrated to play an important role in stabilizing a pentacene derivative by tuning the orbital distribution and lowering the HOMO energy level. This study provides an effective strategy to attain stable acenes without changing the molecular configuration or intermolecular packing structure, and thus improves the potential application of large acenes in electronic devices.
High‐elevation forests are experiencing high rates of warming, in combination with CO2 rise and (sometimes) drying trends. In these montane systems, the effects of environmental changes on tree ...growth are also modified by elevation itself, thus complicating our ability to predict effects of future climate change. Tree‐ring analysis along an elevation gradient allows quantifying effects of gradual and annual environmental changes. Here, we study long‐term physiological (ratio of internal to ambient CO2, i.e., Ci/Ca and intrinsic water‐use efficiency, iWUE) and growth responses (tree‐ring width) of Himalayan fir (Abies spectabilis) trees in response to warming, drying, and CO2 rise. Our study was conducted along elevational gradients in a dry and a wet region in the central Himalaya. We combined dendrochronology and stable carbon isotopes (δ13C) to quantify long‐term trends in Ci/Ca ratio and iWUE (δ13C‐derived), growth (mixed‐effects models), and evaluate climate sensitivity (correlations). We found that iWUE increased over time at all elevations, with stronger increase in the dry region. Climate–growth relations showed growth‐limiting effects of spring moisture (dry region) and summer temperature (wet region), and negative effects of temperature (dry region). We found negative growth trends at lower elevations (dry and wet regions), suggesting that continental‐scale warming and regional drying reduced tree growth. This interpretation is supported by δ13C‐derived long‐term physiological responses, which are consistent with responses to reduced moisture and increased vapor pressure deficit. At high elevations (wet region), we found positive growth trends, suggesting that warming has favored tree growth in regions where temperature most strongly limits growth. At lower elevations (dry and wet regions), the positive effects of CO2 rise did not mitigate the negative effects of warming and drying on tree growth. Our results raise concerns on the productivity of Himalayan fir forests at low and middle (<3,300 m) elevations as climate change progresses.
Himalayan forests are experiencing exceptionally rapid warming during the last decades, yet knowledge on their physiological and growth responses to climate change is limited. Using dendrochronology and tree‐ring stable carbon‐isotope data of Himalayan fir, we found intrinsic water‐use efficiency has increased consistently at all elevations in both dry and wet regions during the past century. Warming has favored tree growth at higher elevations in wet regions, but growth reductions at low/middle elevations in both regions suggest that negative effects of warming and drying overruled positive CO2‐fertilization effects, thus raising concerns on the productivity of Himalayan fir forests under future climate change.
Introducing BN units into polycyclic aromatic hydrocarbons expands the chemical space of conjugated materials with novel properties. However, it is challenging to achieve accurate synthesis of ...BN‐PAHs with specific BN positions and orientations. Here, three new parent B2N2‐perylenes with different BN orientations are synthesized with BN‐naphthalene as the building block, providing systematic insight into the effects of BN incorporation with different orientations on the structure, (anti)aromaticity, crystal packing and photophysical properties. The intermolecular dipole–dipole interaction shortens the π–π stacking distance. The crystal structure, (anti)aromaticity, and photophysical properties vary with the change of BN orientation. The revealed BN doping effects may provide a guideline for the synthesis of BN‐PAHs with specific stacking structures, and the synthetic strategy employed here can be extended toward the synthesis of larger BN‐embedded PAHs with adjustable BN patterns.
A family of parent B2N2‐perylenes with different BN orientations have been synthesized based on the BN‐naphthalene building block. The effects of BN with different orientations on structure, (anti)aromaticity, crystal packing and photophysical properties are systematically investigated. This work provides an efficient synthetic strategy for BN‐PAHs and a deep insight into the structure–property relationship of BN‐PAHs.
Conjugated polymers usually form crystallized and amorphous regions in the solid state simultaneously, making it difficult to accurately determine their precise microstructures. The lack of ...multiscale microstructures of conjugated polymers limits the fundamental understanding of the structure–property relationships in polymer‐based optoelectronic devices. Here, crystals of two typical conjugated polymers based on four‐fluorinated benzodifurandione‐based oligo(p‐phenylene vinylene) (F4BDOPV) and naphthalenediimide (NDI) motifs, respectively, are obtained by a controlled self‐assembly process. The strong diffractivity of the polymer crystals brings an opportunity to determine the crystal structures by combining X‐ray techniques and molecular simulations. The precise polymer packing structures are useful as initial models to evaluate the charge transport properties in the ordered and disordered phases. Compared to the spin‐coated thin films, the highly oriented polymer chains in crystals endow higher mobilities with a lower hopping energy barrier. Microwire crystal transistors of F4BDOPV‐ and NDI‐based polymers exhibit high electron mobilities of up to 5.58 and 2.56 cm2 V−1 s−1, respectively, which are among the highest values in polymer crystals. This work presents a simple method to obtain polymer crystals and their precise microstructures, promoting a deep understanding of molecular packing and charge transport for conjugated polymers.
Conjugated polymer microwire crystals are obtained from solvated aggregates. The precise crystal packing and electronic structure in the polymer microwires are evaluated for understanding of the charge transport properties. Polymer crystal transistors of F4BDOPV‐2T exhibit higher electron mobilities of up to 5.58 cm2 V−1 s−1 with a much lower hopping energy barrier compared with conventional thin‐film transistors.
Because of their resolvable crystal structure, organic conjugated small molecules are intrinsically ideal for elucidating the relationship between microstructures and charge transport properties. It ...has been reported that the charge transport properties depend on molecular structure and molecular packing. In the solid state, π–π stacking of small molecules is significant in the charge transport process. Since π–π stacking of conjugated small molecules is influenced at different degrees by other intra- and intermolecular interactions, as a result, π–π stacking and further the charge transport properties can be controlled or tuned by crystal engineering through precise chemical modification. In this perspective, we give some typical examples illustrating the strategy of controlling π–π stacking in single crystals. Furthermore, we attempt to clarify the complex relationship between π–π stacking and other types of molecular interactions, and its influence on charge transport properties.
Controlling the solution‐state aggregation of conjugated polymers for producing specific microstructures remains challenging. Herein, a practical approach is developed to finely tune the solid‐state ...microstructures through temperature‐controlled solution‐state aggregation and polymer crystallization. High temperature generates significant conformation fluctuation of conjugated backbones in solution, which facilitates the polymer crystallization from solvated aggregates to orderly packed structures. The polymer films deposited at high temperatures exhibit less structural disorders and higher electron mobilities (up to two orders of magnitude) in field‐effect transistors, compared to those deposited at low temperatures. This work provides an effective strategy to tune the solution‐state aggregation to reveal the relationship between solution‐state aggregation and solid‐state microstructures of conjugated polymers.
Using temperature‐controlled polymer aggregation, the solid‐state microstructures of conjugated polymers are finely tuned. The temperature‐controlled strategy enhances the molecular ordering in thin films and leads to efficient charge transport. A polymer transistor with tuned molecular ordering exhibited improved electron mobilities of up to 3.71 cm2 V−1 s−1, which is two orders of magnitude higher than the disordered samples.
Abstract
N-doping plays an irreplaceable role in controlling the electron concentration of organic semiconductors thus to improve performance of organic semiconductor devices. However, compared with ...many mature p-doping methods, n-doping of organic semiconductor is still of challenges. In particular, dopant stability/processability, counterion-semiconductor immiscibility and doping induced microstructure non-uniformity have restricted the application of n-doping in high-performance devices. Here, we report a computer-assisted screening approach to rationally design of a triaminomethane-type dopant, which exhibit extremely high stability and strong hydride donating property due to its thermally activated doping mechanism. This triaminomethane derivative shows excellent counterion-semiconductor miscibility (counter cations stay with the polymer side chains), high doping efficiency and uniformity. By using triaminomethane, we realize a record n-type conductivity of up to 21 S cm
−1
and power factors as high as 51 μW m
−1
K
−2
even in films with thicknesses over 10 μm, and we demonstrate the first reported all-polymer thermoelectric generator.
Low n‐doping efficiency and inferior stability restrict the thermoelectric performance of n‐type conjugated polymers, making their performance lag far behind of their p‐type counterparts. Reported ...here are two rigid coplanar poly(p‐phenylene vinylene) (PPV) derivatives, LPPV‐1 and LPPV‐2, which show nearly torsion‐free backbones. The fused electron‐deficient rigid structures endow the derivatives with less conformational disorder and low‐lying lowest unoccupied molecular orbital (LUMO) levels, down to −4.49 eV. After doping, two polymers exhibited high n‐doping efficiency and significantly improved air stability. LPPV‐1 exhibited a high conductivity of up to 1.1 S cm−1 and a power factor as high as 1.96 μW m−1 K−2. Importantly, the power factor of the doped LPPV‐1 thick film degraded only 2 % after 7 day exposure to air. This work demonstrates a new strategy for designing conjugated polymers, with planar backbones and low LUMO levels, towards high‐performance and potentially air‐stable n‐type polymer thermoelectrics.
Stability: A new rigid coplanar poly(p‐phenylene vinylene) (PPV) derivative, LPPV‐1, is synthesized with a rigid planar backbone and low‐lying LUMO, which lead to reduced conformational disorder and high n‐type doping efficiency. The conductivity of LPPV‐1 is up to 1.1 S cm−1, and the power factor is only 2 % after a 7 day exposure to air. This work represents an effective strategy towards high‐performance and potentially air‐stable n‐type polymer thermoelectrics.
Solution‐processable highly conductive polymers are of great interest in emerging electronic applications. For p‐doped polymers, conductivities as high a nearly 105 S cm−1 have been reported. In the ...case of n‐doped polymers, they often fall well short of the high values noted above, which might be achievable, if much higher charge‐carrier mobilities determined could be realized in combination with high charge‐carrier densities. This is in part due to inefficient doping and dopant ions disturbing the ordering of polymers, limiting efficient charge transport and ultimately the achievable conductivities. Here, n‐doped polymers that achieve a high conductivity of more than 90 S cm−1 by a simple solution‐based co‐deposition method are reported. Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to, and excellent miscibility with, commonly used n‐dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n‐doped polymers, resulting in excellent electrical conductivity and thermoelectric performance.
Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to commonly used n‐dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n‐doped polymers, resulting in excellent electrical conductivity of over 90 S cm−1 and thermoelectric performance up to 106 µW m−1 K−2.
Abstract
Little is known about the transcriptomic plasticity and adaptive mechanisms of circulating tumor cells (CTCs) during hematogeneous dissemination. Here we interrogate the transcriptome of 113 ...single CTCs from 4 different vascular sites, including hepatic vein (HV), peripheral artery (PA), peripheral vein (PV) and portal vein (PoV) using single-cell full-length RNA sequencing in hepatocellular carcinoma (HCC) patients. We reveal that the transcriptional dynamics of CTCs were associated with stress response, cell cycle and immune-evasion signaling during hematogeneous transportation. Besides, we identify chemokine CCL5 as an important mediator for CTC immune evasion. Mechanistically, overexpression of CCL5 in CTCs is transcriptionally regulated by p38-MAX signaling, which recruites regulatory T cells (Tregs) to facilitate immune escape and metastatic seeding of CTCs. Collectively, our results reveal a previously unappreciated spatial heterogeneity and an immune-escape mechanism of CTC, which may aid in designing new anti-metastasis therapeutic strategies in HCC.
PDF
