Durable Ultraflexible Organic Photovoltaics with Novel Metal‐Oxide‐Free Cathode

Flexible and stretchable organic photovoltaics (OPVs) are promising as a power source for wearable devices with multifunctions ranging from sensing to locomotion. Achieving mechanical robustness and high power conversion efficiency for ultraflexible OPVs is essential for their successful application. However, it is challenging to simultaneously achieve these features by the difficulty to maintain stable performance under a microscale bending radius. Ultraflexible OPVs are proposed by employing a novel metal‐oxide‐free cathode that consists of a printed ultrathin metallic transparent electrode and an organic electron transport layer to achieve high electron‐collecting capabilities and mechanical robustness. In fact, the proposed ultraflexible OPV achieves a power conversion efficiency of 9.7% and durability with 74% efficiency retention after 500 cycles of deformation at 37% compression through buckling. The proposed approach can be applied to active layers with different morphologies, thus suggesting its universality and potential for high‐performance ultraflexible OPV devices.     

Hydrolytic Degradation and Monomer Recovery of Poly(butylene succinate) and Poly(butylene succinate/adipate) in the Melt

Aliphatic dicarboxylic acid/aliphatic diol‐derived polyesters, poly(butylene succinate) and poly(butylene succinate/adipate), have been hydrolytically degraded in the melt in high‐temperature and high‐pressure water over a wide temperature range of 180–300 °C for periods of up to 30 min. The formation/decomposition of succinic acid (SA), adipic acid (AA), and butane‐1,4‐diol (BD), plus the molecular weight change of PBS and PBSA were then investigated. SA and AA were recovered at maximum yields of 65–80%, whereas BD was recovered at a maximum yield of only 30%, probably because of its decomposition. The obtained results were compared with those reported for aliphatic hydroxycarboxylic acid‐derived polyesters and aromatic dicarboxylic acid/aliphatic diol‐derived polyesters.

     

Dielectric anisotropy of a homochiral rare-earth metal complex

A homochiral rare-earth metal Tb complex that exhibited a very large dielectric anisotropic property with a temperature-independent feature is obtained. Our findings on high-dielectric anisotropy will provide a new impetus in this field of materials science.     

Asymmetric cyclization-carbonylation of 2-alkyl-2-propargylcyclohexane-1,3-diones: facile access to optically active hydrindanes

Oxidative cyclization-carbonylation of 2-alkyl-2-propargylcyclohexane-1,3-diones mediated by Pd(TFA)₂/2,2′-isopropylidenebis[(4R)-4-(3,4-dimethoxyphenyl)-2-oxazoline] 28 afforded bicyclic-β-alkoxyacrylates in 51-74% yields with 72-82% ee. The products containing quaternary carbon were converted to optically active hydrindanes 33.     

Defect-Free Synthesis of a Fully π-Conjugated Helical Ladder Polymer and Resolution into a Pair of Enantiomeric Helical Ladders**

Fully π-conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically active helical ladder polymer totally composed of achiral units. We now report the defect-free synthesis and resolution of a fully π-conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid-promoted alkyne benzannulations of a rationally designed, random-coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix-inversion barrier, the isolated excess one-handed helical ladder polymer with a degree of polymerization of more than 15 showed a strong circular dichroism with a dissymmetry factor of up to 1.7×10⁻² and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well-supported by molecular dynamics simulation.     

New reactions of a dibenzo[a,e]pentalene

Reduction of dibenzo[a,e]pentalene 3 (denoted as dibenzopentalene hereafter) with excess lithium gave dilithium dibenzopentalenide 1. Since oxidation of 1 with iodine gave 3, redox behavior between 1 and 3 is controllable and reversible. Reaction of 3 with methyllithium gave lithium 5-methyldibenzopentalenide 5, the formation of which was evidenced by some trapping experiments and X-ray crystallographic analysis. Reactions of 3 with halogens gave 5,10-dihalodibenzopentalenes, 8 and 9. Some optical properties of novel dibenzopentalene derivatives are also demonstrated.     

Nanoparticle plasmon-assisted two-photon polymerization induced by incoherent excitation source

We demonstrate the possibility to achieve optical triggering of photochemical reactions via two-photon absorption using incoherent light sources. This is accomplished by the use of arrays of gold nanoparticles, specially tailored with high precision to obtain high near-field intensity enhancement.     

Unique Thermal Structural Phase Transitions Exhibited by Unsymmetrical Organometallic Gold(III)-Dithiolene Complexes with Pentylthio and Hexylthio Groups

Unsymmetrical gold(III)-dithiolene complexes are potential candidates for molecular materials that exhibit thermal structural phase transitions. In this study, unsymmetrical ppy-gold(III) (ppy⁻=C-deprotonated-2-phenylpyridine(−)) complexes [AuC5] and [AuC6] coordinated by dithiolene ligands containing tetrathiafulvalene (TTF) skeletons with pentylthio (2-{bis(pentylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) and hexylthio groups (2-{bis(hexylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) were synthesized. Both complexes exhibited a large absorption band at approximately 508 nm, owing to intramolecular ligand-to-ligand charge transfer. One-dimensional columnar structures with head-to-tail molecular arrangements around the metal ions were constructed in the crystals. The flexible alkylthio groups were intercalated into crystalline spaces between dithiolene ligands in the columns. [AuC5] exhibits a simple phase transition at 198 °C between crystalline and isotropic phases irreversibly. The crystalline phase of [AuC6] observed at 25 °C melted at 148 °C. Another crystalline phase grew above 148 °C with a very slow crystallization rate from the liquid phase and was completely transformed into an isotropic phase at 200 °C.