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We expand the diversity of building blocks available for ionic assembly by introducing tertiary (3 ) ammonium cations into anion complexes. We use proton transfer between 3º amines and organo-phosphoric acids to generate H-bonding cations (R NH+) and anions (RHPO ) that co-assemble with cyanostar macrocycles into assemblies with 2:2:2 stoichiometry. At the heart is a supramolecular dimer where phosphate anions form salt bridges by H-bonding with cations.Unlike conventional ammonium cations,3,000 commercial amines provide diversity for high-throughput screening of 72 combinations (9 nitrogen bases and 8 acids), producing 13 privileged partners for quantitative assembly. Yields depend on the solvent and sterics of salt bridge formation. Ten more nitrogen bases connect to fluorophores (pyrene), photocatalysts (quinoline), drugs (Cipralex, Zytiga), and ionic liquids (imidazole). The synthesis and examination of 82 new salts exemplify how acid-base chemistry can open a pipeline to a diversity of building blocks for exploring hierarchical ionic assembly. 

Magnons are quasiparticles of spin waves, carrying both thermal energy and spin information. Controlling magnon transport processes is critical for developing innovative magnonic devices used in data processing and thermal management applications in microelectronics. The spin ladder compound Sr14Cu24O41 with large magnon thermal conductivity offers a valuable platform for investigating magnon transport. However, there are limited studies on enhancing its magnon thermal conductivity. Herein, we report the modification of magnon thermal transport through partial substitution of strontium with yttrium (Y) in both polycrystalline and single crystalline Sr14−xYxCu24O41. At room temperature, the lightly Y-doped polycrystalline sample exhibits 430% enhancement in thermal conductivity compared to the undoped sample. This large enhancement can be attributed to reduced magnon-hole scattering, as confirmed by the Seebeck coefficient measurement. Further increasing the doping level results in negligible change and eventually suppression of magnon thermal transport due to increased magnon-defect and magnon-hole scattering. By minimizing defect and boundary scattering, the single crystal sample with x = 2 demonstrates a further enhanced room-temperature magnon thermal conductivity of 19Wm−1K−1, which is more than ten times larger than that of the undoped polycrystalline material. This study reveals the interplay between magnon-hole scattering and magnon-defect scattering in modifying magnon thermal transport, providing valuable insights into the control of magnon transport properties in magnetic materials. 

Abstract We report the first conductance measurements of [n]staffane (bicyclopentane) oligomers in single‐molecule junctions. Our studies reveal two quantum transport characteristics unique to staffanes that emerge from their strained bicyclic structure. First, though staffanes are composed of weakly conjugated C−Cσ‐bonds, staffanes carry a shallower conductance decay value (β=0.84±0.02 n⁻¹) than alkane chain analogs (β=0.96±0.03 n⁻¹) when measured with the scanning tunneling microscopy break junction (STM‐BJ) technique. Staffanes are thus more conductive than otherσ‐bonded organic backbones reported in the literature on a per atom basis. Density functional theory (DFT) calculations suggest staffane backbones are more effective conduits for charge transport because their significant bicyclic ring strain destabilizes the HOMO‐2 energy, aligning it more closely with the Fermi energy of gold electrodes as oligomer order increases. Second, the monostaffane is significantly lower conducting than expected. DFT calculations suggest that short monostaffanes sterically enforce insulating gauche interelectrode orientations over syn orientations; these steric effects are alleviated in longer staffanes. Moreover, we find that [2‐5]staffane wires may accommodate axial mechanical strain by “rod‐bending”. These findings show for the first time how bicyclic ring strain can enhance charge transmission in saturated molecular wires. These studies showcase the STM‐BJ technique as a valuable tool for uncovering the stereoelectronic proclivities of molecules at material interfaces. 

Subcomponent self-assembly relies on cation coordination whereas the roles of anions often only emerge during the assembly process. When sites for anions are instead pre-programmed, they have the potential to be used as orthogonal elements to build up structure in a predictable and modular way. We explore this idea by combining cation (M + ) and anion (X − ) binding sites together and show the orthogonal and modular build up of structure in a multi-ion assembly. Cation binding is based on a ligand (L) made by subcomponent metal-imine chemistry (M + = Cu + , Au + ) while the site for anion binding (X − = BF 4 − , ClO 4 − ) derives from the inner cavity of cyanostar (CS) macrocycles. The two sites are connected by imine condensation between a pyridyl-aldehyde and an aniline-modified cyanostar. The target assembly [LM-CS-X-CS-ML], + generates two terminal metal complexation sites (LM and ML) with one central anion-bridging site (X) defined by cyanostar dimerization. We showcase modular assembly by isolating intermediates when the primary structure-directing ions are paired with weakly coordinating counter ions. Cation-directed (Cu + ) or anion-bridged (BF 4 − ) intermediates can be isolated along either cation–anion or anion–cation pathways. Different products can also be prepared in a modular way using Au + and ClO 4 − . This is also the first use of gold( i ) in subcomponent self-assembly. Pre-programmed cation and anion binding sites combine with judicious selection of spectator ions to provide modular noncovalent syntheses of multi-component architectures.