Extraordinary Redox Activities in Ladder-Type Conjugated Molecules Enabled by B ← N Coordination-Promoted Delocalization and Hyperconjugation.

The introduction of B ← N coordinate bond-isoelectronic to C-C single bond-into π-systems represents a promising strategy to impart exotic redox and electrochromic properties into conjugated organic molecules and macromolecules. To achieve both reductive and oxidative activities using this strategy, a cruciform ladder-type molecular constitution was designed to accommodate oxidation-active, reduction-active, and B ← N coordination units into a compact structure. Two such compounds (BN-F and BN-Ph) were synthesized via highly efficient N-directed borylation. These molecules demonstrated well-separated, two reductive and two oxidative electron-transfer processes, corresponding to five distinct yet stable oxidation states, including a rarely observed boron-containing radical cation. Spectroelectrochemical measurements revealed unique optical characteristics for each of these reduced/oxidized species, demonstrating multicolor electrochromism with excellent recyclability. Distinct color changes were observed between each redox state with clear isosbestic points on the absorption spectra. The underlying redox mechanism was elucidated by a combination of computational and experimental investigations. Single-crystal X-ray diffraction analysis on the neutral state, the oxidized radical cation, and the reduced dianion of BN-Ph revealed structural transformations into two distinct quinonoid constitutions during the oxidation and reduction processes, respectively. B ← N coordination played an important role in rendering the robust and reversible multistage redox properties, by extending the charge and spin delocalization, by modulating the π-electron density, and by a newly established hyperconjugation mechanism

Alternative Donor--Acceptor Stacks from Crown Ethers and Naphthalene Diimide Derivatives: Rapid, Selective Formation from Solution and Solid State Grinding

Self assembling {pi}-conjugated molecules into ordered structures are of increasing interest in the field of organic electronics. One particular example is charge transfer complexes containing columnar alternative donor-acceptor (ADA) stacks, where neutral and ionic ground states can be readily tuned to modulate electrical, optical, and ferroelectrical properties. Aromatic-aromatic and charge transfer interactions have been the leading driving forces in assisting the self-assembly of ADA stacks. Various folding structures containing ADA stacks were assembled in solution with the aid of solvophobic or ion-binding interactions. Meanwhile, examples of solid ADA stacks, which are more appealing for practical use in devices, were obtained from cocrystalization of binary components or mesophase assembly of liquid crystals in bulk blends. Regardless of these examples, faster and more controllable approaches towards precise supramolecular order in the solid state are still highly desirable

Enhanced Stability of Janus Nanoparticles by Covalent Cross-Linking of Surface Ligands

A mercapto derivative of diacetylene was used as the hydrophilic ligand to prepare Janus nanoparticles by using hydrophobic hexanethiolate-protected gold (AuC6, diameter 5 nm) nanoparticles as the starting materials. The amphiphilic surface characters of the Janus nanoparticles were verified by contact angle measurements, as compared to those of the bulk-exchange counterparts where the two types of ligands were distributed rather homogeneously on the nanoparticle surface. Dynamic light scattering studies showed that the Janus nanoparticles formed stable superstructures in various solvent media that were significantly larger than those by the bulk-exchange counterparts. This was ascribed to the amphiphilic characters of the Janus nanoparticles that rendered the particles to behave analogously to conventional surfactant molecules. Notably, because of the close proximity of the diacetylene moieties on the Janus nanoparticle surface, exposure to UV irradiation led to effective covalent cross-linking between the diacetylene moieties of neighboring ligands, as manifested in UV–vis and fluorescence measurements where the emission characteristics of dimers and trimers of diacetylene were rather well-defined, in addition to the monomeric emission. In contrast, for bulk-exchange nanoparticles, no trimer emission could be identified, and the intensity of dimer emission was markedly lower (though the intensity increased with increasing diacetylene coverage on the particle surface) under the otherwise identical experimental conditions. This is largely because the diacetylene ligands were distributed on the entire particle surface, and it was difficult to find a large number of ligands situated closely so that the stringent topochemical principles for the polymerization of diacetylene derivatives could be met. Importantly, the cross-linked Janus nanoparticles were found to exhibit marked enhancement of the structural integrity, which was attributable to the impeded surface diffusion of the thiol ligands on the nanoparticle surface, as manifested in fluorescence measurements of aged nanoparticles

4,4′-([4,4′-Bipyridine]-1,1′-diium-1,1′-diyl)dibenzoate dihydrate

We report here the synthesis of a neutral viologen derivative, C24H16N2O4·2H2O. The non-solvent portion of the structure (Z-Lig) is a zwitterion, consisting of two positively charged pyridinium cations and two negatively charged carboxylate anions. The carboxylate group is almost coplanar [dihedral angle = 2.04 (11)°] with the benzene ring, whereas the dihedral angle between pyridine and benzene rings is 46.28 (5)°. The Z-Lig molecule is positioned on a center of inversion (Fig. 1). The presence of the twofold axis perpendicular to the c-glide plane in space group C2/c generates a screw-axis parallel to the b axis that is shifted from the origin by 1/4 in the a and c directions. This screw-axis replicates the molecule (and solvent water molecules) through space. The Z-Lig molecule links to adjacent molecules via O—H...O hydrogen bonds involving solvent water molecules as well as intermolecular C—H...O interactions. There are also π–π interactions between benzene rings on adjacent molecules

Performing Hazard Analyses and Setting Triggers for Reevaluation in Lab-Scale Chemical Reactions

Laboratory chemical synthesis research typically lacks the preplanned hazard responses found in production-scale industrial laboratories. Chemical safety management is a known challenge in education-based facilities, which is concerning for academic and national laboratory environments working with inexperienced student researchers. At the Molecular Foundry, a U.S. Department of Energy (DOE) user facility, a chemical safety management form has been developed that follows DOE’s Integrated Safety Management (ISM) process, which evaluates the risks and hazards associated with all forms of work. An ISM form for chemical synthesis is described here in detail. It is regularly used to guide chemical safety discussions between researchers and supervisors, to plan accident responses, and to establish triggers, at which point a reevaluation of the work is needed. The form makes it straightforward to know what limits researchers may work within and makes it clear which procedure changes will require a new safety assessment and discussion before work continues. The ISM form for synthesis is being successfully used in three fields of chemistry: Inorganic, Organic, and Biological. The form has also been adapted for liquid sample preparation in electron microscopy. Upper management, supervisors, students, and general users are engaged in this process. It is hoped that sharing this knowledge will enable educational institutions and other laboratories to develop similar methods to help researchers and supervisors understand the hazards as well as the working limits of any protocol, helping researchers to work more independently and safely within the laboratory

Rational tuning of high-energy visible light absorption for panchromatic small molecules by a two-dimensional conjugation approach.

We have demonstrated a rational two-dimensional (2D) conjugation approach towards achieving panchromatic absorption of small molecules. By extending the conjugation on two orthogonal axes of an electron acceptor, namely, bay-annulated indigo (BAI), the optical absorptions could be tuned independently in both high- and low-energy regions. The unconventional modulation of the high-energy absorption is rationalized by density functional theory (DFT) calculations. Such a 2D tuning strategy provides novel guidelines for the design of molecular materials with tailored optoelectronic properties

Rational tuning of high-energy visible light absorption for panchromatic small molecules by a two-dimensional conjugation approach.

We have demonstrated a rational two-dimensional (2D) conjugation approach towards achieving panchromatic absorption of small molecules. By extending the conjugation on two orthogonal axes of an electron acceptor, namely, bay-annulated indigo (BAI), the optical absorptions could be tuned independently in both high- and low-energy regions. The unconventional modulation of the high-energy absorption is rationalized by density functional theory (DFT) calculations. Such a 2D tuning strategy provides novel guidelines for the design of molecular materials with tailored optoelectronic properties

An Omics Approach to Mixed-Anion Electrolyte Discovery for Lithium Metal Batteries for Electric Aircraft

Here, we advance an omics approach to understand how lithium salts in locally super-concentrated electrolytes (LSCEs) should be mixed to create stable ionically conductive interphases in high-power Li|NMC811 cells charged to high voltage. Mixed-anion LCSEs maintain an areal ion flux of 6 mA cm–2 during discharge across 500 cycles with 70% capacity retention, outperforming single-salt LSCEs as well as single- and dual-salt concentrated electrolytes. These advantages stem from the enrichment of cathode–electrolyte interphases with fluoroethers, which suppress cathode corrosion and fracturing

Chain-Growth Sulfur(VI) Fluoride Exchange Polycondensation: Molecular Weight Control and Synthesis of Degradable Polysulfates.

Sulfur(VI) fluoride exchange (SuFEx) click chemistry has offered a facile and reliable approach to produce polysulfates and polysulfonates. However, the current SuFEx polymerization methods lack precise control of target molecular weight and dispersity. Herein, we report the first chain-growth SuFEx polycondensation process by exploiting the unique reactivity and selectivity of S-F bonds under SuFEx catalysis. Given the higher reactivity of iminosulfur oxydifluoride versus fluorosulfate, the chain-growth SuFEx polycondensation is realized by using an iminosulfur oxydifluoride-containing compound as the reactive chain initiator and deactivated AB-type aryl silyl ether-fluorosulfates bearing an electron-withdrawing group as monomers. When 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was utilized as the polymerization catalyst, precise control over the polymer molecular weight and polydispersity was achieved. The resulting polymers possess great thermal stability but are easily degradable under mild acidic and basic conditions