Synergistic topological and supramolecular control of Diels-Alder reactivity based on a tunable self-complexing host-guest molecular switch.

Compartmentalization and binding-triggered conformational change regulate many metabolic processes in living matter. Here, we have synergistically combined these two biorelevant processes to tune the Diels-Alder (DA) reactivity of a synthetic self-complexing host-guest molecular switch CBPQT4+ -Fu, consisting of an electron-rich furan unit covalently attached to the electron-deficient cyclobis(paraquat-p-phenylene) tetrachloride (CBPQT4+ , 4Cl- ) host. This design allows CBPQT4+ -Fu to efficiently compartmentalize the furan ring inside its host cavity in water, thereby protecting it from the DA reaction with maleimide. Remarkably, the self-complexed CBPQT4+ -Fu can undergo a conformational change through intramolecular decomplexation upon the addition of a stronger binding molecular naphthalene derivative as a competitive guest, triggering the DA reaction upon addition of a chemical regulator. Remarkably, connecting the guest to a thermoresponsive lower critical solution temperature (LCST) copolymer regulator controls the DA reaction on command upon heating and cooling the reaction media beyond and below the cloud point temperature of the copolymer, representing a rare example of decreased reactivity upon increasing temperature. Altogether, this work opens up new avenues towards combined topological and supramolecular control over reactivity in synthetic constructs, enabling control over reactivity through molecular regulators or even mild temperature variations.

Self-Assembled Molecules for Hole-Selective Electrodes in Highly Stable and Efficient Inverted Perovskite Solar Cells with Ultralow Energy Loss.

Good selective contacts are necessary for solar cells that are efficient and have long-term stability. Since 1998, with the advent of solid-state dye sensitized solar cells (DSSC), Spiro-OMeTAD has become the reference hole-transporting material. Yet, for efficient solar cells Spiro-OMeTAD must be partially oxidized with chemical dopants, which compromises the long-term stability of the solar cell. Alternatively, semiconductor polymers such as PTAA have been also studied, matching or improving the solar cell characteristics. However, PTAA-based devices lack long-term stability. Moreover, both Spiro-OMeTAD and PTAA are expensive materials to synthesize. Hence, approaches toward increasing the solar cell stability without compromising the device efficiency and decreasing the manufacturing cost are very desirable. In this work we have modified Spiro-OMeTAD, by an easy-to-use methodology, by introducing a carboxylic acid anchoring group (Spiro-Acid), thereby allowing the formation of self-assembled monolayers (SAMs) of the hole-transporting material in dopant-free p-i-n hybrid perovskite solar cells (iPSCs). The resulting device showed a champion efficiency of 18.15% with ultralow energy loss, which is the highest efficiency among Spiro-OMeTAD-based iPSCs, and a remarkable fill factor of over 82%, as well as excellent long-term illumination stability. Charge transfer and charge carrier dynamics are studied by using advanced transient techniques to understand the interfacial kinetics. Our results demonstrate that the Spiro-OMeTAD-based SAMs have a great potential in producing low-cost iPSC devices, due to lower material usage, good long-term stability, and high performance.

A Self-Assembling Flavin for Visible Photooxidation.

A new flavin-based gelator is reported which forms micellar structures at high pH and gels at low pH. This flavin can be used for the photooxidation of thiols under visible light, with the catalytic efficiency being linked to the self-assembled structures present.

Chiral Quantum Metamaterial for Hypersensitive Biomolecule Detection.

Chiral biological and pharmaceutical molecules are analyzed with phenomena that monitor their very weak differential interaction with circularly polarized light. This inherent weakness results in detection levels for chiral molecules that are inferior, by at least six orders of magnitude, to the single molecule level achieved by state-of-the-art chirally insensitive spectroscopic measurements. Here, we show a phenomenon based on chiral quantum metamaterials (CQMs) that overcomes these intrinsic limits. Specifically, the emission from a quantum emitter, a semiconductor quantum dot (QD), selectively placed in a chiral nanocavity is strongly perturbed when individual biomolecules (here, antibodies) are introduced into the cavity. The effect is extremely sensitive, with six molecules per nanocavity being easily detected. The phenomenon is attributed to the CQM being responsive to significant local changes in the optical density of states caused by the introduction of the biomolecule into the cavity. These local changes in the metamaterial electromagnetic environment, and hence the biomolecules, are invisible to "classical" light-scattering-based measurements. Given the extremely large effects reported, our work presages next generation technologies for rapid hypersensitive measurements with applications in nanometrology and biodetection.

Benzo-Dipteridine Derivatives as Organic Cathodes for Li- and Na-ion Batteries.

Organic-based electrodes for Li- and Na-ion batteries present attractive alternatives to commonly applied inorganic counterparts which can often carry with them supply-chain risks, safety concerns with thermal runaway, and adverse environmental impact. The ability to chemically direct the structure of organic electrodes through control over functional groups is of particular importance, as this provides a route to fine-tune electrochemical performance parameters. Here, we report two benzo-dipteridine derivatives, BF-Me2 and BF-H2 , as high-capacity electrodes for use in Li- and Na-ion batteries. These moieties permit binding of multiple Li-ions per molecule while simultaneously ensuring low solubility in the supporting electrolyte, often a precluding issue with organic electrodes. Both display excellent electrochemical stability, with discharge capacities of 142 and 182 mAh g-1 after 100 cycles at a C/10 rate and Coulombic efficiencies of 96% and ∼ 100% demonstrated for BF-Me2 and BF-H2 , respectively. The application of a Na-ion cell has also been demonstrated, showing discharge capacities of 88.8 and 137 mAh g-1 after 100 cycles at a C/2 rate for BF-Me2 and BF-H2 , respectively. This work provides an encouraging precedent for these and related structures to provide versatile, high-energy density, and long cycle-life electrochemical energy storage materials.

An investigation of the roles furan versus thiophene π-bridges play in donor-π-acceptor porphyrin based DSSCs.

Dye-sensitized solar cells (DSSCs) continue to attract interest due to their lower cost production compared to silicon based solar cells and their improving power conversion efficiencies. Porphyrin-based sensitizers have become an important sub-class due to their strong absorption characteristics in the visible region, convenient modulation of properties through synthetic manipulation and class-leading power conversion efficiencies. In this article, we report the synthesis and characterization of two porphyrin-based dyes and their application as sensitizers in DSSCs. A thiophene and a furan moiety have been incorporated into the push-pull architecture as a π-bridge, allowing the systematic investigation of how these moieties influence the physical properties of the dyes and the performance of their resulting DSSCs. A significant difference in PCEs has been observed, with the furan containing dye (PorF, PCE = 4.5%) being more efficient than the thiophene-based analogue (PorT, PCE = 3.6%) in conjunction with the iodide/triiodide redox electrolyte.