The highly efficient single-junction bulk-heterojunction (BHJ) PM6:Y6 system can achieve high open circuit voltages (V OC) while maintaining exceptional fill-factor (FF) and short-circuit current (J SC) values. With a low energetic offset, the blend system was found to exhibit radiative and nonradiative recombination losses that are among the lower reported values in the literature. Recombination and extraction dynamic studies revealed that the device shows moderate nongeminate recombination coupled with exceptional extraction throughout the relevant operating conditions. Several surface and bulk characterization techniques were employed to understand the phase separation, long-range ordering, as well as donor:acceptor (D:A) inter-and intramolecular interactions at an atomic-level resolution. This was achieved using photo-conductive atomic force microscopy (pc-AFM), grazing incidence wide angle x-ray scattering (GIWAXS), and solid-state 19 F Magic-Angle Spinning (MAS) NMR spectroscopy. The synergy of multifaceted characterization and device physics was used to uncover key insights, for the first time, on the structure-property relationships of this high performing BHJ blend. Detailed information about atomically resolved D:A interactions and packing revealed that the high performance of over 15% efficiency in this blend can be correlated to a beneficial morphology that allows high J SC and FF to be retained despite the low energetic offset.

Supramolecular hydrogels derived from natural products have promising applications in diagnostics, drug delivery, and tissue engineering. We studied the formation of a long-lived hydrogel made by mixing guanosine (G, 1) with 0.5 equiv of KB(OH)4. This ratio of borate anion to ligand is crucial for gelation as it links two molecules of 1, which facilitates cation-templated assembly of G4·K(+) quartets. The guanosine-borate (GB) hydrogel, which was characterized by cryogenic transmission electron microscopy and circular dichroism and (11)B magic-angle-spinning NMR spectroscopy, is stable in water that contains physiologically relevant concentrations of K(+). Furthermore, non-covalent interactions, such as electrostatics, π-stacking, and hydrogen bonding, enable the incorporation of a cationic dye and nucleosides into the GB hydrogel.

Some fundamental questions in the organic solar cell (OSC) community are related to the role of bulk and interfacial morphology on key processes such as charge generation, recombination, and extraction...

The ability to modulate the physical properties of a supramolecular hydrogel may be beneficial for biomaterial and biomedical applications. We find that guanosine (G 1), when combined with 0.5 equiv of potassium borate, forms a strong, self-supporting hydrogel with elastic moduli >10 kPa. The countercation in the borate salt (MB(OH)4) significantly alters the physical properties of the hydrogel. The gelator combination of G 1 and KB(OH)4 formed the strongest hydrogel, while the weakest system was obtained with LiB(OH)4, as judged by (1)H NMR and rheology. Data from powder XRD, (1)H double-quantum solid-state magic-angle spinning (MAS) NMR and small-angle neutron scattering (SANS) were consistent with a structural model that involves formation of borate dimers and G4·K(+) quartets by G 1 and KB(OH)4. Stacking of these G4·M(+) quartets into G4-nanowires gives a hydrogel. We found that the M(+) cation helps stabilize the anionic guanosine-borate (GB) diesters, as well as the G4-quartets. Supplementing the standard gelator mixture of G 1 and 0.5 equiv of KB(OH)4 with additional KCl or KNO3 increased the strength of the hydrogel. We found that thioflavin T fluoresces in the presence of G4·M(+) precursor structures. This fluorescence response for thioflavin T was the greatest for the K(+) GB system, presumably due to the enhanced interaction of the dye with the more stable G4·K(+) quartets. The fluorescence of thioflavin T increased as a function of gelator concentration with an increase that correlated with the system's gel point, as measured by solution viscosity.

An NMR crystallography study of the hemihydrate of 2', 3'-O-isopropylidineguanosine (Gace) is presented, together with powder X-ray diffraction and thermogravimetric analysis. (1)H double-quantum and (14)N-(1)H HMQC spectra recorded at 850MHz and 75kHz MAS (using a JEOL 1mm probe) are presented together with a (1)H-(13)C refocused INEPT spectrum recorded at 500MHz and 12.5kHz MAS using eDUMBO-122(1)H homonuclear decoupling. NMR chemical shieldings are calculated using the GIPAW (gauge-including projector augmented wave) method; good two-dimensional agreement between calculation and experiment is observed for (13)C and (1)H chemical shifts for directly bonded CH and CH3 peaks. There are two Gace molecules in the asymmetric unit cell: differences in specific (1)H chemical shifts are rationalised in terms of the strength of CH-π and intermolecular hydrogen bonding interactions.

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Characterizing the density of states (DOS) width accurately is critical in understanding the charge-transport properties of organic semiconducting materials as broader DOS distributions lead to an inferior transport. From a morphological standpoint, the relative densities of ordered and disordered regions are known to affect charge-transport properties in films; however, a comparison between molecular structures showing quantifiable ordered and disordered regions at an atomic level and its impact on DOS widths and charge-transport properties has yet to be made. In this work, for the first time, the DOS distribution widths of two model conjugated polymer systems are characterized using three different techniques. A quantitative correlation between energetic disorder from band-bending measurements and charge transport is established, providing direct experimental evidence that chargecarrier mobility in disordered materials is compromised due to the relaxation of carriers into the tail states of the DOS. Distinction and quantification of ordered and disordered regions of thin films at an atomic level is achieved using solid-state NMR spectroscopy. An ability to compare solid-state film morphologies of organic semiconducting polymers to energetic disorder, and in turn charge transport, can provide useful guidelines for applications of organic conjugated polymers in pertinent devices.

The molecular level interface engineering with a multifunctional ligand 2,5-thiophenedicarboxylic acid suppresses interfacial ion diffusion and inhibits I2 formation, which leads to high operational stability with T80 of 3570 h along with PCE of 23.4%.