For investigation of structure-property relationships in copper phosphine halide complexes, treatment of copper(I) halides with chiral bis(phosphines) gave dinuclear [Cu((R,R)-i-Pr-DuPhos)(μ-X)] [X = I (1), Br (2), Cl (3)], [Cu(μ-((R,R)-Me-FerroLANE)(μ-I)] (5), and [Cu((S,S)-Et-FerroTANE)(I)] (6), pentanuclear cluster CuI((S,S)-Et-FerroTANE) (7), and the monomeric Josiphos complexes Cu((R,S)-CyPF-t-Bu)(I) (8) and Cu((R,S)-PPF-t-Bu)(I) (9); 1-3, 5, and 7-9 were structurally characterized by X-ray crystallography. Treatment of iodide 1 with AgF gave [Cu((R,R)-i-Pr-DuPhos)(μ-F)] (4). DuPhos complexes 1-4 emitted yellow-green light upon UV irradiation at room temperature in the solid state. This process was studied by low-temperature emission spectroscopy and density functional theory (DFT) calculations, which assigned the luminescence to (M + X)LCT (CuX to DuPhos aryl) excited states. Including Grimme's dispersion corrections in the DFT calculations (B3LYP-D3) gave significantly shorter Cu-Cu distances than those obtained using B3LYP, with the nondispersion-corrected calculations better matching the crystallographic data; other intramolecular metrics are better reproduced using B3LYP-D3. A discussion of the factors leading to this unusual observation is presented.

The phenomenon of quantum confinement in hybrid low-dimensional lead-free perovskite derivatives continues to hinder the development of these materials for electron carrier devices such as next-generation solar cells. Spatial separation of metal− halide octahedra within crystal structures yields materials with greater moisture and photodegradation resistance, but at the expense of desired photophysical properties such as small band gaps. We report the synthesis and characterization of an unexplored isomorphic series of perovskite derivatives consisting of isolated dimeric metal−halide M 2 X 10 4− (M = In, Sb; X = Cl, Br) anions charge-balanced with halopyridinium cations. Assembly of these species results in a supramolecular network via extensive noncovalent interactions and may be described as a pseudo-zero-dimensional arrangement. Despite the low dimensionality, these materials display semiconductive optical band-gap energies owing to the appearance of an intermediate band due to hybridization of metal−halide atomic and molecular orbitals. Low-temperature luminescence measurements provide evidence of electron delocalization where photoexcited metal/halide electrons are captured by organic cations via energetically accessible π* molecular orbitals, separating electron/hole pairs. Natural bonding orbital (NBO) calculations reveal that metal hybridization is more pronounced in compounds containing Sb 3+ and can be influenced by noncovalent interactions between anionic and cationic building units.

Reported are the syntheses and characterization of six new heterometallic UO2 2+ /Pb 2+ compounds. These materials feature rare instances of M-oxo interactions, which influence bonding properties of the uranyl cation. The spectroscopic effects of these interactions were measured using diffuse reflectance, luminescence and Raman spectroscopy. Computational density functional theory (DFT) based natural bonding orbital (NBO) and quantum theory of atoms in molecules (QTAIM) methods indicate interactions arise predominantly through charge transfer between cationic units via the electron donating uranyl O sp x lone pair orbitals and electron accepting Pb 2+ p orbitals. The interaction strength varies as a function of Pb-oxo interaction distance and angle with energy values ranging from ranging from 0.47 kcal/mol in the longer contacts to 21.94 kcal/mol in the shorter contacts. Uranyl units with stronger interactions display an asymmetric bond weakening and a loss of covalent character in the U=O bonds interacting closely with the Pb 2+ ion. Luminescence quenching is observed in cases where strong Pb-oxo interactions are present, and is accompanied by significant red-shifting of the uranyl symmetric Raman stretch. Changes to inner sphere uranyl bonding manifest as a weakening of the U=O bond as a result of interaction with the Pb 2+ ion. http://www.ccdc.cam.ac.uk/data_reque st/cif.Crystallography Tables, PXRD, Luminescence Data at 78K, additional NBO and QTAIM data, DFT models (pdf)X-ray data for compound 1 (CIF) X-ray data for compound 2 (CIF) X-ray data for compound 3 (CIF) X-ray data for compound 4 (CIF) X-ray data for compound 5 (CIF) X-ray data for compound 6 (CIF)

A new bismuth(III)−organic compound, Hphen-[Bi 2 (HPDC) 2 (PDC) 2 (NO 3 )]•4H 2 O (Bi-1; PDC = 2,6-pyridinedicarboxylate and phen = 1,10-phenanthroline), was synthesized, and the structure was determined by single-crystal X-ray diffraction. The compound was found to display bright-bluegreen phosphorescence in the solid state under UV irradiation, with a luminescent lifetime of 1.776 ms at room temperature. The room temperature and low-temperature (77 K) emission spectra exhibited the vibronic structure characteristic of Hphen phosphorescence. Time-dependent density functional theory studies showed that the excitation pathway arises from an energy transfer from the dimeric structural unit to Hphen, with participation from a ninecoordinate Bi center. The triplet state of Hphen is believed to be stabilized via supramolecular interactions, which, when coupled with the heavy-atom effect induced by Bi, leads to the observed longlived luminescence. The compound displayed a solid-state quantum yield of over 27%. To the best of our knowledge, this is the first such compound to exhibit phenanthrolinium phosphorescence with such long-lived, room temperature lifetimes in the solid state. To further elucidate the energy-transfer mechanism, Ln 3+ (Ln = Eu, Tb, Sm) ions were successfully doped into the parent compound, and the resulting materials exhibited dual emission from Hphen and Ln, promoting tunability of the emission color.

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.

Reported is the synthesis characterization of eight new halotellurate(IV) compounds consisting of isolated [TeX6]2- (X = Cl, Br) octahedra charge balanced by halopyridinium (XPy; X = H, Cl, Br, I)...

Five novel tetravalent thorium (Th) compounds that consist of Th­(H2O) x Cl y structural units were isolated from acidic aqueous solutions using a series of nitrogen-containing heterocyclic hydrogen (H) bond donors. Taken together with three previously reported phases, the compounds provide a series of monomeric ThIV complexes wherein the effects of noncovalent interactions (and H-bond donor identity) on Th structural chemistry can be examined. Seven distinct structural units of the general formulas [Th­(H2O) x Cl8–x ] x−4 (x = 2, 4) and [Th­(H2O) x Cl9–x ] x−5 (x = 5–7) are described. The complexes range from chloride-deficient [Th­(H2O)7Cl2]2+ to chloride-rich [Th­(H2O)2Cl6]2– species, and theory was used to understand the relative energies that separate complexes within this series via the stepwise chloride addition to an aquated Th cation. Electronic structure theory predicted the reaction energies of chloride addition and release of water through a series of transformations, generally highlighting an energetic driving force for chloride complexation. To probe the role of the counterion in the stabilization of these complexes, electrostatic potential (ESP) surfaces were calculated. The ESP surfaces indicated a dependence of the chloride distribution about the Th metal center on the pK a of the countercation, highlighting the directing effects of noncovalent interactions (e.g., Hbonding) on Th speciation.

Evaporative co-crystallization of MCl (M = Na, K, Rb, Cs) with BiOCl in aqueous HCl produces double salts: M x Bi y Cl (x+3y) •zH 2 O. The sodium salt, Na 2 BiCl 5 •5H 2 O (monoclinic P2 1 /c, a = 8.6983(7) Å, b = 21.7779(17) Å, c = 7.1831(6) Å, β= 103.0540(10)°, V = 1325.54(19) Å 3 , Z = 4) is composed of zigzag chains of µ 2-Cl-cis-linked (BiCl 5) n 2nchains. Edge-sharing chains of NaCl n (OH 2) 6−n octahedra (n = 0, 2, 3) are linked through µ 3-Cl to Bi. The potassium salt, K 7 Bi 3 Cl 16 (trigonal R−3c, a = 12.7053(9) Å, b = 12.7053(9) Å, c = 99.794(7) Å, V = 13951(2) Å 3 , Z = 18) contains (Bi 2 Cl 10) 4edge-sharing dimers of octahedra and simple (BiCl 6) 3octahedra. The K + ions are 5-to 8-coordinate and the chlorides are 3-, 4-, or 5-coordinate. The rubidium salt, Rb 3 BiCl 6 •0.5H 2 O (orthorhombic Pnma, a = 12.6778(10) Å, b = 25.326(2) Å, c = 8.1498(7) Å, V = 2616.8(4) Å 3 , Z = 8) contains (BiCl 6) 3octahedra. The Rb + ions are 6-, 8-, and 9-coordinate, and the chlorides are 4-or 5-coordinate. Two cesium salts were formed: Cs 3 BiCl 6 (orthorhombic Pbcm, a = 8.2463(9) Å, b = 12.9980(15) Å, c = 26.481(3) Å, V = 2838.4(6) Å 3 , Z = 8) being comprised of (BiCl 6) 3octahedra, 8-coordinate Cs + , and 3-, 4-, and 5-coordinate Cl −. In Cs 3 Bi 2 Cl 9 (orthorhombic Pnma, a = 18.4615(15) Å, b = 7.5752(6) Å, c = 13.0807(11) Å, V = 1818.87(11) Å 3 , Z = 4) Bi octahedra are linked by µ 2-bridged Cl into edge-sharing Bi 4 squares which form zigzag (Bi 2 Cl 9) n 3nladders. The 12-coordinate Cs + ions bridge the ladders, and the Cl − ions are 5-and 6-coordinate. Four of the double salts are weakly photoluminescent at 78 K, each showing a series of three excitation peaks near 295, 340, and 380 nm and a broad emission near 440 nm.