This paper refines the nature of the interactions between electron-deficient arenes and halide anions. Conclusions are based on (i) new crystal structures containing alkali halide salts with 1,2,4,5-tetracyanobenzene (TCB) and 18-crown-6, (ii) evaluation of crystal structures found in the Cambridge Structural Database, and (iii) MP2/aug-cc-pVDZ calculations of F-, Cl-, and Br- complexes with TCB, 1,3,5-tricyanobenzene, triazine, and hexafluorobenzene. When the halide lies above the plane of the π system, the results establish that three distinctly different types of complexes are possible:  strongly covalent σ complexes, weakly covalent donor−π-acceptor complexes, and noncovalent anion−π complexes. When aryl C−H groups are present, a fourth type of interaction leads to C−H · · · X- hydrogen bonding. Characterization of the different geometries encountered with the four possible binding motifs provides criteria needed to design host architectures containing electron-deficient arenes.

Doped metal oxide nanocrystals that exhibit tunable localized surface plasmon resonances (LSPRs) represent an intriguing class of nanomaterials that show promise for a variety of applications from spectroscopy to sensing. LSPRs arise in these materials through the introduction of aliovalent dopants and lattice oxygen vacancies. Tuning the LSPR shape and energy is generally accomplished through controlling the concentration or identity of dopants in a nanocrystal, but the lack of finer synthetic control leaves several fundamental questions unanswered regarding the effects of radial dopant placement, size, and nanocrystalline architecture on the LSPR energy and damping. Here, we present a layer-by-layer synthetic method for core/shell nanocrystals that permits exquisite and independent control over radial dopant placement, absolute dopant concentration, and nanocrystal size. Using Sn-doped InO (ITO) as a model LSPR system, we synthesized ITO/InO core/shell as well as InO/ITO core/shell nanocrystals with varying shell thickness, and investigated the resulting optical properties. We observed profound influence of radial dopant placement on the energy and linewidth of the LSPR response, noting (among other findings) that core-localized dopants produce the highest values for LSPR energies per dopant concentration, and display the lowest damping in comparison to nanocrystals with shell-localized or homogeneously distributed dopants. Inactive Sn dopants present on ITO nanocrystal surfaces are activated upon the addition of a subnanometer thick undoped InO shell. We show how LSPR energy can be tuned fully independent of dopant concentration, relying solely on core/shell architecture. Finally, the impacts of radial dopant placement on damping, independent of LSPR energy, are explored.

1H NMR spectroscopic data and complementary theoretical predictions suggest that a designed receptor exhibits the anion-pi interaction in solution.

A unique ligand design allows the formation of both an M L triple helicate and an M L tetrahedron (M=Ti, Ga; L=ligand based on 2,6-diaminoanthracene). Although the tetrahedron is entropically disfavored, a strong host-guest interaction with Me N is enough to drive the equilibrium towards the tetrahedron. Remarkably, the helicate can be quantitatively converted into the tetrahedron simply by addition of Me N (shown schematically).