Pyridine ligand complexes of [Bu4N][BiI4] were prepared using chelating ligands 2,2′‐bipyridyl (2,2′‐Bpy), 1,10‐phenanthroline (Phen), and 4‐nitro‐1,10‐phenanthroline (NO2Phen), producing monomeric complexes [Bu4N][(2,2′‐Bpy)BiI4], [Bu4N][(Phen)BiI4], and [Bu4N][(NO2Phen)BiI4], and bridging ligands 4,4′‐bipyridyl (4,4′‐Bpy), pyrazine (Pyz), and aminopyrazine (NH2Pyz) resulting in formation of polymers [Bu4N]n[(4,4′‐Bpy)BiI4]n and [Bu4N]2n[(RPyz)Bi2I8]n (R = H, NH2). The latter contain edge‐sharing Bi2I8 dimers. Organic ligand BiIII/CuI clusters [Bu4N]2[L2Bi2Cu2I10] {L = PPh3, P(OPh)3} and [Bu4N]2[PyBi2Cu2I10] (Py = pyridine) have been prepared. All bismuthate(III) centers are distorted octahedra and all cuprate(I) centers are tetrahedral, with organic ligands bonded to CuI. The first neutral BiI3/CuI organic ligand complex [BiCu3I6(PPh3)6] is reported. Diffuse reflectance spectroscopy measurements reveal strong absorption bands for both iodobismuthate(III) and iodocuprate(I)/bismuthate(III) complexes in the UV and visible range. Despite the similarity in absorption bands, DFT calculations support a distinct shift in transition from a mixed halide/metal‐to‐ligand charge transfer (X/MLCT) to a metal–halide cluster‐centered transition upon incorporation of copper(I) into the cluster.

A series of mer‐[Ln(NO3)3(Ph3PO)3] complexes were prepared from Ln(NO3)3·xH2O and Ph3PO in chloroform (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, and Er). The La and Nd complexes were 0.25 CHCl3 solvates, whereas the others were solvent‐free. The identical reaction using Yb(NO3)3·xH2O produced the unique salt trans‐[Yb(NO3)2(Ph3PO)4][Yb(NO3)4(Ph3PO)]·Et2O. All nitrate ions in all complexes are η2‐chelating. A comparison of the various [Ln(NO3)3(Ph3PO)3] structures, including those in the literature, reveals at least four common polymorphs, each of which is represented by isomorphic structures of multiple Ln ions. Luminescence of mer‐[Ln(NO3)3(Ph3PO)3] (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, and Dy), trans‐[Yb(NO3)2(Ph3PO)4][Yb(NO3)4(Ph3PO)] and Ph3PO assignments are reported. Latva's empirical rule allows for the antenna effect, in which energy is transferred from the triplet state of the Ph3PO ligand, to occur only for Tb3+. Excitation via Ph3PO results in strong green luminescence for Tb3+ having twice the intensity as that which results from direct excitation of the f‐f transitions.

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The reaction of copper(I) iodide (CuI) and N-alkyl pyridinium (RPy + , R = H, Me, Et, n -propyl = Pr, n -butyl = Bu, n -pentyl = Pn, and n -hexyl = Hx) or N-butyl-3-substituted pyridinium (N-Bu-3-PyX + , X = I, Br, Cl, CN, and OMe) iodide salts yielded pyridinium iodocuprate(I) salts. Crystal structures of iodocuprate ions coupled with RPy + include {Cu 3 I 6 3– } n (R = H), {Cu 2 I 3 – } n (R = Me), {Cu 3 I 4 – } n (R = Et), {Cu 6 I 8 2– } n (R = Pr), and {Cu 5 I 7 2– } n (R = Bu, Pn, Hx). The [N-Bu-3-PyX] + ions were typically paired with the 1-D chain {Cu 5 I 7 2– } n . Diffuse reflectance spectroscopy performed on the [N-Bu-3-PyX] + iodocuprate salts revealed that increasing the electron withdrawing capacity of the [N-Bu-3-PyX] + system reduced the absorption edge of the iodocuprate salt. Variable temperature emission spectra of several [N-Bu-3-PyX] + compounds revealed two emission peaks, one consistent with a cluster-centered halide to metal charge transfer and the other consistent with an intermolecular mixed halide/metal charge transfer to the organic cation. The emission intensity and emission wavelength of the mixed halide/metal to cation charge transfer depends on the organic cation substitution.

We report on the vapochromic behavior of a series of homo- and heterometallic copper(i) iodide/silver(i) iodide nanoparticles when exposed to dimethyl sulfide (DMS) vapor.