Solvent effects on oxygen-17 chemical shifts in methyl formate: linear solvation shift relationships

A multiple linear regression analysis has been carried out using the Kamlet-Abboud-Taft solvatochromic parameters in order to quantify the solvent effects on the (17)O chemical shifts of methyl formate (MF). The influence of the solvents upon the carbonyl oxygen chemical shifts is smaller for MF than for N-methylformamide (NMF). The influence (in parts per million) of the solvent polarity-polarizability reduces from -21.9pi* in amides to -9.6pi* in MF. The influence of the solvent hydrogen-bond-donor acidities reduces from -42.0alpha in formamides to -16.9alpha in MF. The solvent effects upon the dicoordinated oxygen chemical shifts of MF are smaller in magnitude and opposite in direction, i.e., 4.8pi* and 2.6alpha, than those for the carbonyl oxygen. (17)O hydration shifts have been calculated for the NMF + (H(2)O)(6) and MF + (H(2)O)(5) complexes by the ab initio GIAO method at the 6-311 + G** level. The hydration shifts calculated for the carbonyl oxygens of NMF and MF and for the dicoordinated oxygen of MF, -102.4, -64.7, and 17.6 ppm, respectively, show the same trend as the corresponding empirical hydration shifts, -101.7, -42.0, and 14.2 ppm.     

Regulating the morphology of fluorinated non-fullerene acceptor and polymer donor via binary solvent mixture for high efficiency polymer solar cells

Fluorinated non-fullerene acceptors(NFAs) usually have planar backbone and a higher tendency to crystallize compared to their non-fluorinated counterparts, which leads to enhanced charge mobility in organic solar cells(OSCs). However, this selforganization behavior may result in excessive phase separation with electron donors and thereby deteriorate device efficiency.Herein, we demonstrate an effective approach to tune the molecular organization of a fluorinated NFA(INPIC-4 F), and its phase separation with the donor PBDB-T, by varying the casting solvent. A prolonged film drying time encourages the crystallization of INPIC-4 F into spherulites and consequently results in excessive phase separation, leading to a low device power conversion efficiency(PCE) of 8.1%. Contrarily, a drying time leads to fine mixed domains with inefficient charge transport properties,resulting in a moderate device PCE of 11.4%. An intermediate film drying time results in the formation of face-on π-π stacked PBDB-T and INPIC-4 F domains with continuous phase-separated networks, which facilitates light absorption, exciton dissociation as well as balanced charge transport towards the electrode, and achieves a remarkable PCE of 13.1%. This work provides a rational guide for optimizing the molecular ordering of NFAs and electron donors for high device efficiency.     

A New Class of Blue‐Emitting Materials for LED Applications: Triarylamine N‐Functionalised 2,7‐Linked Carbazole Polymers

Attachment of triarylamino‐functional groups at the 9‐position of 2,7‐linked carbazole polymers results in blue‐emitting materials with two independent redox processes that were attributed to the triarylamino groups and the polymer backbone, respectively. This new class of blue‐emitting conjugated polymers was prepared via a Suzuki cross‐coupling reaction and showed low turn‐on voltages in electroluminescent devices as a result of their low ionisation potentials. The photophysical, electrochemical and electroluminescent properties of these materials are discussed.