The superiority of isomeric, fluorination and curtailed π-conjunction on A-D-A type acceptors for organic photovoltaics.

The performance of organic solar cell (OSC) devices has been significantly enhanced by the dramatic evolution of A-D-A type non-fullerene acceptors (NFAs). Nevertheless, the structure-property-performance relationship of NFAs in the OSC device is unclear. Here, the intrinsic design factors of isomeric, fluorination and π-conjunction curtailing on the photophysical properties of benzodi (thienopyran) (BDTP) (named NBDTP-M, NBDTTP-M, NBDTP-Fin, and NBDTP-Fout)-based NFAs are discussed. The results show that fluorination on the terminal group of NBDTP-Fout could effectively decrease the highest occupied orbital (HOMO) energy level and the lowest unoccupied orbital (LUMO) energy level. And the long π-conjugated donor unit for NBDTTP-M could increase the HOMO energy level and bring a small HOMO-LUMO energy bandgap. Meanwhile, the substitution of external oxygen atoms and the fluorine atoms in the terminal group could introduce positive changes to the electrostatic potential of the NBDTP-Fout, favouring the charge separation at the donor/acceptor interface. Moreover, the structural design of external oxygen atom substitution, fluorination on the terminal group and curtailed π-conjugated donor unit could decrease the electron vibration-coupling of exciton diffusion, exciton dissociation and electronic transfer processes. The suppression of the exciton decay and charge recombination in those high-performance NFAs indicate that the investigated molecular designs could be effective for further improvement of OSCs.

Multicolor Luminescence of a Polyurethane Derivative Driven by Heat/Light-Induced Aggregation.

The study of aggregate formation and its controllable effect on luminescence behavior has a far-reaching influence in establishing a universal aggregation photophysical mechanism. In this paper, we obtained clusters with different extents of aggregation by heat-induced or light-triggered aggregation of a new polyurethane derivative (PUE). The controllable regulation of multicolor fluorescence of a single (nondoped) polymeric material is realized. The luminescence behavior of PUE varies with microscopic control of the aggregation structure. Compared with the powder state, the enhanced atom-atom and group-group interactions of PUE-gel effectively limit the nonradiative transitions in the excited state and result in a red-shift in emission. This work avoids complex organic synthesis and demonstrates a simple strategy to induce aggregation and regulate the emitting color of macromolecules, providing a template for developing new materials for multicolor fluorescence. In addition, a pattern was constructed with encryption, anticounterfeiting, and information transmission functions which provide a proof-of-concept demonstration of the practical potential of PUE as a smart material.

Effect of co-inoculation with arbuscular mycorrhizal fungi and phosphate solubilizing fungi on nutrient uptake and photosynthesis of beach palm under salt stress environment.

Beach plum (Prunus maritima) is an ornamental plant, famous for its strong salt and drought stress tolerance. However, the poor growth rate of transplanted seedlings has seriously restricted its application in salinized soil. This study investigated the effects of inoculation with arbuscular mycorrhizal fungus (AMF), Funneliformis mosseae, and phosphate-solubilizing fungus (PSF), Apophysomyces spartima, on the growth, nutrient (N, P, and K) uptake, and photosynthesis of beach plum under saline (170 mM NaCl) and non-saline (0 mM NaCl) conditions. We aimed to find measures to increase the growth rate of beach plum in saline-alkali land and to understand the reasons for this increase. The results showed that salinization adversely affected colonization by AMF but positively increased PSF populations (increased by 33.9-93.3% over non-NaCl treatment). The dual application of AMF and PSF mitigated the effects of salt stress on all growth parameters and nutrient uptake, significantly for roots (dry weight and P and N contents increased by 91.0%, 68.9%, and 40%, respectively, over non-NaCl treatment). Salinization caused significant reductions in net photosynthetic rate (Pn), stomatal conductance (Gs), transpiration rate (E), and intercellular CO2 concentration (Ci) value, while inoculation with AMF and PSF inoculations significantly abated such reductions. The maximum efficiency of photosystem II (PSII) (Fv/Fm), the photochemical quenching coefficient (qP), and the nonphotochemical quenching (NPQ) values were affected little by inoculation with AMF, PSF, or both under non-NaCl treatments. However, plants inoculated with AMF and/or PSF had higher Fv/Fm, qP, and ФPSII values (increased by 72.5-188.1%) than the control under NaCl treatment, but not a higher NPQ value. We concluded that inoculation with AMF or PSF increased nutrient uptake and improved the gas-exchange and Chl fluorescence parameters of beach plum under salt stress environment. These effects could be strengthened by the combination of AMF and PSF, especially for nutrient uptake, root growth, and Pn, thereby alleviating the deleterious effects of NaCl stress on beach plum growth.

Supramolecular Oligourethane Gel with Multicolor Luminescence Controlled by Mechanically Sensitive Hydrogen-Bonding.

We report a new type of mechanically sensitive multicolor luminescent oligourethane gel (OUA-gel). The conformation of the oligomeric chains can be controlled by changing the strength of hydrogen bonds. The optical properties of the oligomers are highly dependent on the conformations which vary in response to mechanical stresses and phase transitions. The design relies on the introduction of a single mechanical chromophore, aurintricarboxylic acid, with propeller-like, spatially crowded, and highly twisted conformations, and the presence of three carboxyl groups, which provide multidirectional hydrogen-bonding opportunities. Introducing dimethylsulfoxide (DMSO) as an additional H-bond acceptor molecule leads to a viscous OUA-gel which exhibits multiemission colors because of changes in the chain conformation within the matrix, which are induced by different strengths of H bonds. The conformation can be adjusted by mechanical force or temperature, both of which influence the H-bonding. The multifunctional and multicolored mechanochromism of the OUA-gel has great promise in sensing applications. The results represent a substantial step toward understanding the mechanism of polychromism in soft materials and the molecular design of advanced smart materials.

Two Ni/Co-substituted sandwich-type germanomolybdates based on an unprecedented trivacant polyanion [α-GeMo10O36]8.

Two Ni/Co-substituted sandwich-type germanomolybdates, {[M3(NH2-trz)6(H2O)6][M4(H2O)2(HGeMo10O36)2]}·nH2O (M = Ni2+ (1) and Co2+ (2), n = 10 (1) or 11 (2), NH2-trz = 4-amino-1,2,4-triazole), have been obtained under hydrothermal conditions. 1 and 2 represent the first trivacant Keggin germanomolybdates involving unprecedented [α-GeMo10O36]8- fragments and {M3O4} quasi-cubane building units. Both of them exhibit electrocatalytic behaviours for H2O2 reduction and photocatalytic properties for CO2 conversion.