Nonhalogenated Solvent Processable and High-Density Photopatternable Polymer Semiconductors Enabled by Incorporating Hydroxyl Groups in the Side Chains.

Polymer semiconductors hold tremendous potential for applications in flexible devices, which is however hindered by the fact that they are usually processed by halogenated solvents rather than environmentally more friendly solvents. An effective strategy to boost the solubility of high-performance polymer semiconductors in nonhalogenated solvents such as tetrahydrofuran (THF) by appending hydroxyl groups in the side chains is herein presented. The results show that hydroxyl groups, which can be easily incorporated into the side chains, can significantly improve the solubility of typical p- and n-types as well as ambipolar polymer semiconductors in THF. Meanwhile, the thin films of these polymer semiconductors from the respective THF solutions show high charge mobilities. With THF as the processing and developing solvents these polymer semiconductors with hydroxyl groups in the side chains can be well photopatterned in the presence of the photo-crosslinker, and the charge mobilities of the patterned thin films are mostly maintained by comparing with those of the respective pristine thin films. Notably, THF is successfully utilized as the processing and developing solvent to achieve high-density photopatterning with ≈82 000 device arrays cm-2 for polymer semiconductors in which hydroxyl groups are appended in the side chains.

Intrinsically Stretchable and Healable Polymer Semiconductors.

In recent decades, polymer semiconductors, extensively employed as charge transport layers in devices like organic field-effect transistors (OFETs), have undergone thorough investigation due to their capacity for large-area solution processing, making them promising for mass production. Research efforts have been twofold: enhancing the charge mobilities of polymer semiconductors and augmenting their mechanical properties to meet the demands of flexible devices. Significant progress has been made in both realms, propelling the practical application of polymer semiconductors in flexible electronics. However, integrating excellent semiconducting and mechanical properties into a single polymer still remains a significant challenge. This review intends to introduce the design strategies and discuss the properties of high-charge mobility stretchable conjugated polymers. In addition, another key challenge faced in this cutting-edge field is maintaining stable semiconducting performance during long-term mechanical deformations. Therefore, this review also discusses the development of healable polymer semiconductors as a promising avenue to improve the lifetime of stretchable device. In conclusion, challenges and outline future research perspectives in this interdisciplinary field are highlighted.

Solar Efficiency of Azo-Photoswitches for Energy Conversion: A Comprehensive Assessment.

Photoswitches can absorb solar photons and store them as chemical energy by photoisomerization, which is regarded as a promising strategy for photochemical solar energy storage. Although many efforts have been devoted to photoswitch discovery, the solar efficiency, a critical fundamental parameter assessing the solar energy conversion ability, has attracted little attention and remains to be studied comprehensively. Here we provide a systematic evaluation of the solar efficiency of typical azo-switches including azobenzenes and azopyrazoles, and gain a comprehensive understanding on its decisive factors. All the efficiencies are found below 1.0 %, far from the proposed limits for molecular solar thermal energy storage systems. Azopyrazoles exhibit remarkably higher solar efficiencies (0.59-0.94 %) than azobenzenes (0.11-0.43 %), benefiting from largely improved quantum yield and photoisomerization yield. Light filters can be used to improve the isomerization yield but inevitably narrow the usable range of solar spectrum, and these two contradictory effects ultimately reduce solar efficiencies. We envision this conflict could be resolved through developing azo-switches that afford high isomerization yields by absorbing wide-spectrum solar energy. We hope this work could promote more efforts to improve the solar efficiency of photoswitches, which is highly relevant to the prospect for future applications.

A rechargeable molecular solar thermal system below 0 °C.

An optimal temperature is crucial for a broad range of applications, from chemical transformations, electronics, and human comfort, to energy production and our whole planet. Photochemical molecular thermal energy storage systems coupled with phase change behavior (MOST-PCMs) offer unique opportunities to capture energy and regulate temperature. Here, we demonstrate how a series of visible-light-responsive azopyrazoles couple MOST and PCMs to provide energy capture and release below 0 °C. The system is charged by blue light at -1 °C, and discharges energy in the form of heat under green light irradiation. High energy density (0.25 MJ kg-1) is realized through co-harvesting visible-light energy and thermal energy from the environment through phase transitions. Coatings on glass with photo-controlled transparency are prepared as a demonstration of thermal regulation. The temperature difference between the coatings and the ice cold surroundings is up to 22.7 °C during the discharging process. This study illustrates molecular design principles that pave the way for MOST-PCMs that can store natural sunlight energy and ambient heat over a wide temperature range.

(Hetero)arylazo-1,2,3-triazoles: "Clicked" Photoswitches for Versatile Functionalization and Electronic Decoupling.

The development of light-responsive chemical systems often relies on the rational design and suitable incorporation of molecular photoswitches such as azobenzenes. Linking a photoswitch core with another π-conjugated molecular entity may give rise to intramolecular electronic coupling, which can dramatically impair the photoswitch function. Decoupling strategies have been developed based on additionally inserting a linker that can disrupt the through-bond electronic communication. Here we show that 1,2,3-triazole-a commonly used decoupling spacer-can be directly merged into the azoswitch core to construct a class of "self-decoupling" azoswitches called (hetero)arylazo-1,2,3-triazoles. Such azotriazole photoswitches are easily accessed and modularly functionalized by click chemistry. Their photoswitch property can be optimized by rational design of the substituent groups or heteroaryl rings, allowing (near-)quantitative E⇆Z photoisomerization yields and tunable Z-isomer thermal half-lives from days to years. Combined experimental and theoretical results demonstrate that the electronic structure of the photoswitch core is not substantially affected by various substituents attached to the 1,2,3-triazole unit, benefiting from its cross-conjugated nature. The combination of clickable synthesis, tunable photoswitch property, and self-decoupling ability makes (hetero)arylazo-1,2,3-triazoles intriguing molecular tools in developing photoresponsive systems with desired performance.

Azobispyrazole Family as Photoswitches Combining (Near-) Quantitative Bidirectional Isomerization and Widely Tunable Thermal Half-Lives from Hours to Years*.

Azobenzenes are classical molecular photoswitches that have been widely used. In recent endeavors of molecular design, replacing one or both phenyl rings with heteroaromatic rings has emerged as a strategy to expand molecular diversity and access improved photoswitching properties. Many mono-heteroaryl azo molecules with unique structures and/or properties have been developed, but the potential of bis-heteroaryl architectures is far from fully exploited. We report a family of azobispyrazoles, which combine (near-)quantitative bidirectional photoconversion and widely tunable Z-isomer thermal half-lives from hours to years. The two five-membered rings remarkably weaken the intramolecular steric hindrance, providing new possibilities for engineering the geometric and electronic structure of azo photoswitches. Azobispyrazoles generally exhibit twisted Z-isomers that facilitate complete Z→E photoisomerization, and their thermal stability can be broadly adjusted regardless of the twisted shape, overcoming the conflict between photoconversion (favored by the twisted shape) and Z-isomer stability (favored by the orthogonal shape) encountered by mono-heteroaryl azo switches.

Permethylation Introduces Destructive Quantum Interference in Saturated Silanes.

The single-molecule conductance of silanes is suppressed due to destructive quantum interference in conformations with cisoid dihedral angles along the molecular backbone. Yet, despite the structural similarity, σ-interference effects have not been observed in alkanes. Here we report that the methyl substituents used in silanes are a prerequisite for σ-interference in these systems. Through density functional theory calculations, we find that the destructive interference is not evident to the same extent in nonmethylated silanes. We find the same is true in alkanes as the transmission is significantly suppressed in permethylated cyclic and bicyclic alkanes. Using scanning tunneling microscope break-junction method we determine the single-molecule conductance of functionalized cyclohexane and bicyclo[2.2.2]octane that are found to be higher than that of equivalent permethylated silanes. Rather than the difference between carbon and silicon atoms in the molecular backbones, our calculations reveal that it is primarily the difference between hydrogen and methyl substituents that result in the different electron transport properties of nonmethylated alkanes and permethylated silanes. Chemical substituents play an important role in determining the single-molecule conductance of saturated molecules, and this must be considered when we improve and expand the chemical design of insulating organic molecules.

Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes.

Linear silanes are efficient molecular wires due to strong σ-conjugation in the transoid conformation; however, the structure-function relationship for the conformational dependence of the single-molecule conductance of silanes remains untested. Here we report the syntheses, electrical measurements, and theoretical characterization of four series of functionalized cyclic and bicyclic silanes including a cyclotetrasilane, a cyclopentasilane, a bicyclo[2.2.1]heptasilane, and a bicyclo[2.2.2]octasilane, which are all extended by linear silicon linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated (bi)cyclic silanes is dominated by a single path through the molecule and is controlled by the dihedral angles along this path. This strong sensitivity to molecular conformation dictates the single-molecule conductance of σ-conjugated silanes and allows for systematic control of the conductance through molecular design.

Comprehensive suppression of single-molecule conductance using destructive σ-interference.

The tunnelling of electrons through molecules (and through any nanoscale insulating and dielectric material 1 ) shows exponential attenuation with increasing length 2 , a length dependence that is reflected in the ability of the electrons to carry an electrical current. It was recently demonstrated3-5 that coherent tunnelling through a molecular junction can also be suppressed by destructive quantum interference 6 , a mechanism that is not length-dependent. For the carbon-based molecules studied previously, cancelling all transmission channels would involve the suppression of contributions to the current from both the π-orbital and σ-orbital systems. Previous reports of destructive interference have demonstrated a decrease in transmission only through the π-channel. Here we report a saturated silicon-based molecule with a functionalized bicyclo[2.2.2]octasilane moiety that exhibits destructive quantum interference in its σ-system. Although molecular silicon typically forms conducting wires 7 , we use a combination of conductance measurements and ab initio calculations to show that destructive σ-interference, achieved here by locking the silicon-silicon bonds into eclipsed conformations within a bicyclic molecular framework, can yield extremely insulating molecules less than a nanometre in length. Our molecules also exhibit an unusually high thermopower (0.97 millivolts per kelvin), which is a further experimental signature of the suppression of all tunnelling paths by destructive interference: calculations indicate that the central bicyclo[2.2.2]octasilane unit is rendered less conductive than the empty space it occupies. The molecular design presented here provides a proof-of-concept for a quantum-interference-based approach to single-molecule insulators.

Experimental and modeling analysis of asymmetrical on-off oscillation in coupled non-identical inverted bottle oscillators.

Upside-down bottles containing water which are common in our daily life exhibit rich vibration dynamics. Rich dynamic regimes are observed in bottle oscillators by directly measuring the pressure difference between inside and outside of a bottle with the aid of pressure sensors. We observe experimentally that an asymmetrical oscillation process between the outflow of water and the inflow of air is formed in a single bottle oscillator and, in addition, a kind of 2:1 frequency synchronization occurs in a coupled system of two non-identical bottle oscillators. The peak values of the oscillation of pressure differences between inside and outside of the bottle decease as the height of the liquid surface steps down, while the oscillation period increases gradually. The theoretical model of the oscillator is amended to understand the regimes in the experiment by introducing time-dependent parameters related to the asymmetrical oscillation processes. Our numerical results based on the model fit well with the experimental ones.

Conformations of cyclopentasilane stereoisomers control molecular junction conductance.

Here we examine the impact of ring conformation on the charge transport characteristics of cyclic pentasilane structures bound to gold electrodes in single molecule junctions. We investigate the conductance properties of alkylated cyclopentasilane cis and trans stereoisomers substituted in the 1,3-position with methylthiomethyl electrode binding groups using both the scanning tunneling microscope-based break junction technique and density functional theory based ab initio calculations. In contrast with the linear ones, these cyclic silanes yield lower conductance values; calculations reveal that the constrained dihedral geometries occurring within the ring are suboptimal for σ-orbital delocalization, and therefore, conductance. Theoretical calculations reproduce the measured conductance trends for both cis and trans isomers and find several distinct conformations that are likely to form stable molecular junctions at room temperature. Due to the weakened σ-conjugation in the molecule, through-space interactions are found to contribute significantly to the conductance. This manuscript details the vast conformational flexibility in cyclopentasilanes and the tremendous impact it has on controlling conductance.