The reaction of Pt(IPr)(SnBu^t₃)(H), 1 [IPr = N-heterocyclic carbene ligand N,N’-bis-(2,6-(diisopropyl) phenyl)imidazole-2-ylidene], 2 with Ru­₅(µ₅-C)(CO)₁₅, 3, Fe₃(CO)₁₂, 4, and Ru₃(CO)₁₂, 5, afforded several mixed-metal Pt-Ru and Pt-Fe cluster complexes. The reaction between 1 and 2 in benzene reflux in 1.2:1 (and 2.2:1) ratio afforded monoplatinum-pentaruthenium complexes PtRu­₅(IPr)(µ₆-C)(CO)₁₅, 6, in 54% (10%) yield, and PtRu­₅(IPr)(µ₆-C)(CO)₁₄(H)₂, 7, in 6% (10%) yield, as well as Pt₂Ru₅(IPr)(µ₆-C)(CO)₁₅, 8, and diplatinum-pentaruthenium Pt₂Ru₅(IPr)₂(µ₆-C)(CO)₁₅, 9, in 2% (36%) yield. Compound 6 readily reacts with, H₂ in room temperature to form 7, while 9 shows dynamic activity in solution with Pt(IPr) ligands exchanging . The reaction of 1 and 3 in benzene at room temperature in a 3:1 ratio, produced two mixed-metal trigonal planar Pt-Fe complexes a monoplatinum-diiron Fe₂Pt(IPr)(CO)₉, 10, in 20% yield and diplatinum-monoiron FePt₂(IPr)₂(CO)₆, 11, in 2% yield. The carbonylation of 10 shows full consumption to compound 11. In a 3:1 ratio, 1 and 5 were mixed in hexane at reflux temperature affording the trigonal bipyramidal cluster Pt₂Ru₃(IPr)₂(CO)₁₂, 12, in 32% yield. The synthesis, reactivity, and structural characterization of the complexes will be discussed.

Taking advantage of inorganic click (iClick) and aurophilic interactions complexes {[PEt₃Au]₂(μ-N₃C₂)-9,9-dioctyl-9H-fluorene}₂ (Au₄-FO) and [PPh₃Au]₂(μ-N₃C₂)-9,9-dioctyl-9H-fluorene (Au₂-FO) were inserted into OLEDs to give voltage dependent light. Varying the voltage and percent of Au present in the OLED yields light that has the colors white, blue, red, and green as confirmed using 1931 CIE color space. Au₄-FO and Au₂-FO were synthesized via iClick and exhibit both fluorescence and phosphorescence in solution and in the device. The device was fabricated with the structure ITO/PEDOT:PSS/PVK:PBD:Au/LiF/Al. The turn on voltage ranged depending on the percent of Au present in the emissive layer, the lowest voltage observed was 14 V.

Although salicylaldimine (salen) ligands are ubiquitous in coordination and organometallic chemistry, much less work has been conducted with the phosphinimine (RN=PR₃) analogues. Thus, we have prepared a series of hexadentate phosphazidosalen and tetradentate phosphasalen ligands via reaction between the vicinal diazide 1,2-diazidobenzene and the requisite phosphine. The alkali metal salts of these scaffolds react with UCl₄(dme)₂ to afford a range of uranium complexes that feature unusual structures and bonding. Intriguingly, we observed stepwise N₂ elimination from the phosphazidosalen complex with concomitant U–Cl bond activation. The synthesis, structures and reaction chemistry of these species will be discussed in detail.

Heavy metals present in contaminated water sources present a significant threat to humans and wildlife alike. The development of new materials to efficiently remove targeted heavy metal toxins from aquatic environments is essential to securing the future of our already stressed potable water supplies. Previous efforts in the development of materials for heterogeneous water purification and remediation have relied upon highly porous (eg activated charcoal) or functionalized materials (eg layered double hydroxides). In this work, we aimed to design and synthesize highly porous and water-stable metal-organic frameworks (MOFs) with embedded basic sites using hard-soft acid-base theory. A series of five UiO-66-based MOFs were synthesized, characterized, and analyzed for water stability and heavy metal uptake capabilities in order to probe the role of thiol and thioether functionalities within a porous MOF toward heavy metal capture and selectivity. Two of the newly synthesized MOFs exhibit exceptional stability, even to exposure to strongly acidic and basic environments, and >97% removal of Ag(I) from aqueous solutions. Another material exhibits >98% removal of Hg(II).

Boric acid flux reactions with lanthanide and actinide trichlorides have yielded new structures and insights into the kinetic products of the f-borates. These reactions proceeded at significantly lower temperatures than previous experiments and for a much shorter duration. We have determined that the first neodymium kinetic product is a previously-reported acentric tetraborate chloride. The second kinetic product is a neodymium hexaborate chloride which is analogous to a series of lanthanide hexaborate bromides. An isomorphous americium hexaborate chloride has been obtained as the first kinetic product in the americium chloride-boric acid system. The second americium borate phase is isomorphous with a known samarium borate, and is notable for excluding all chlorides which were present in the starting material. These americium borates were obtained under identical reaction conditions, suggesting a small thermodynamic difference. This presentation will discuss the new structures and the order in which the neodymium, plutonium, and americium borates form.

The search for polynuclear metal complexes (or clusters) with new structural motifs and interesting properties, such as magnetic, optical and catalytic, continues to attract the interest of the academic community for a number of reasons. These include, but are not limited to: (i) the synthesis of nanoscale molecular materials with large nuclearities and unique structures, (ii) the isolation of high-spin molecules and single-molecule magnets (SMMs) with large spin ground state values (S) and energy barriers (U) for the magnetization reversal, and (iii) the synthesis of molecular magnetic refrigerants with enhanced magnetocaloric properties as alternatives to low-temperature cooling applications. Highly anisotropic systems resulting from the presence of metal ions with unquenched orbital angular momenta, i.e., 4f-metal ions such as Dy^III and Tb^III, may lead to prominent SMMs with large blocking temperatures and U values. In this work, we have decided to combine lanthanides (Ln) with various 3d-metal ions, under different reaction conditions, as a means of obtaining high-nuclearity heterometallic 3d/4f-metal clusters with unique structures, large S values and interesting SMM properties. To this end, several new families of {M₆Ln₆} (M²⁺ = divalent metal ions), {Cu₆Ln₁₂}, {Mn₆Ln₄} will be discussed in detail.