title: Sb@Ni12@Sb20-/+and Sb@Pd12@Sb20nCluster Anions, Where n = +1, -1, -3, -4: Multi-Oxidation-State Clusters of Interpenetrating Platonic Solids.
abstract: K5Sb4and K3Sb7Zintl ion precursors react with Pd(PPh3)4in ethylenediamine/toluene/PBu4+solutions to give crystals of Sb@Pd12@Sb20n-/PBu4+salts, where n = 3, 4. The clusters are structurally identical in the two charge states, with nearly perfect Ihpoint symmetry, and can be viewed as an Sb@Pd12icosahedron centered inside of an Sb20dodecahedron. The metric parameters suggest very weak Sb-Sb and Pd-Pd interactions with strong radial Sb-Pd bonds between the Sb20and Pd12shells. All-electron DFT analysis shows the 3- ion to be diamagnetic with Ihsymmetry and a 1.33 eV HOMO-LUMO gap, whereas the 4- ion undergoes a Jahn-Teller distortion to an S = 1/2 D3dstructure with a small 0.1 eV gap. The distortion is predicted to be small and is not discernible by crystallography. Laser desorption-ionization time-of-flight mass spectrometry (LDI-TOF MS) studies of the crystalline samples show intense parent Sb@Pd12@Sb20-ions (negative ion mode) and Sb@Pd12@Sb20+(positive ion mode) along with series of Sb@Pd12-y@Sb20-x-/+ions. Ni(cyclooctadiene)2reacts with K3Sb7in en/tol/Bu4PBr solvent mixtures to give black precipitates of Sb@Ni12@Sb20n-salts that give similar Sb@Ni12@Sb20-/+parent ions and Sb@Ni12-y@Sb20-x-/+degradation series in the respective LDI-TOF MS studies. The solid-state and gas-phase studies of the icosahedral Sb@M12@Sb20n-/n+ions show that the clusters can exist in the -4, -3, -1, +1 (M = Pd) and +1, -1 (M = Ni) oxidation states. These multiple-charge-state clusters are reminiscent of redox-active fullerenes (e.g., C60n, where n = +1, 0, -1, -2, -3, -4, -5, -6).
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
authors.forename: Yi
authors.identifier: 0000-0001-9866-2376
authors.initials: Y
authors.lastname: Wang
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
authors.forename: Melanie
authors.identifier: 0000-0003-0382-0824
authors.initials: M
authors.lastname: Moses-DeBusk
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
authors.forename: Lauren
authors.initials: L
authors.lastname: Stevens
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
authors.forename: Junkai
authors.identifier: 0000-0001-8135-8343
authors.initials: J
authors.lastname: Hu
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
authors.forename: Peter
authors.initials: P
authors.lastname: Zavalij
authors.affiliation: Departments of Chemistry and Materials Science, Johns Hopkins University , Baltimore, Maryland 21218, United States.
authors.forename: Kit
authors.initials: K
authors.lastname: Bowen
authors.affiliation: U.S. Naval Research Laboratory , Codes 6189 and 6877, Washington, D.C. 20375-5347, United States.
authors.forename: Brett I
authors.initials: BI
authors.lastname: Dunlap
authors.affiliation: U.S. Naval Research Laboratory , Codes 6189 and 6877, Washington, D.C. 20375-5347, United States.
authors.forename: Evan R
authors.initials: ER
authors.lastname: Glaser
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland , College Park, Maryland 20742, United States.
authors.forename: Bryan
authors.initials: B
authors.lastname: Eichhorn