Friday May 5th – Presentations

In by admin



Vincent Zollo Jr.1, Anjaneyulu Koppaka1, Sedigheh Etezadi1, Burjor Captain1.

1. Department of Chemistry, University of Miami, Coral Gables, FL 33124, USA

08:30 AM
to 08:50 AM
Inorganic Chemistry

The reaction of Pt(IPr)(SnBut3)(H), 1 [IPr = N-heterocyclic carbene ligand N,N’-bis-(2,6-(diisopropyl) phenyl)imidazole-2-ylidene], 2 with Ru­55-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)26-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.

Voltage dependent light emitters from iClick and aurophilic interactions

Christopher. C. Beto,1 Ethan. D. Holt,1 Yajing Yang,1 James. D. Bullock,Charles W. Zeman,1  Ion Ghiviriga,1 Kirk S. Schanze,2* and Adam S. Veige1*

1University of Florida, Department of Chemistry, Center for Catalysis, P.O. Box 117200, Gainesville, FL, 32611
2University of Texas at San Antionio, Department of Chemistry, One UTSA Circle, San Antonio, TX 78249

08:50 AM
to 09:10 AM
Inorganic Chemistry

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.

Designing New Scaffolds for Organoactinide Chemistry: Synthesis, Characterization and Reactivity of Phosphazide and Phosphasalen Ligands

Paul G. Hayes, Connor S. MacNeil, Tara K. K. Dickie, Christopher P. Forfar

University of Lethbridge
Department of Chemistry & Biochemistry
4401 University Drive, Lethbridge, Alberta, Canada T1K 3M4

09:10 AM
to 09:45 AM
Inorganic Chemistry

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)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.

Metal-organic frameworks with embedded basic sites for heavy metal capture from aquatic environments

Trevor A. Makal

The University of Virginia's College at Wise

10:15 AM
to 10:35 AM
Inorganic Chemistry

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).


Alexander T. Chemey and Thomas E. Albrecht-Schmitt

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA

10:35 AM
to 10:55 AM
Inorganic Chemistry

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.

High-Nuclearity 3d/4f-Metal Complexes with Aesthetically-Pleasing Structures and Single-Molecule Magnetism Properties

Dimitris I. Alexandropoulos,1 Luis Cunha-Silva,2 George Christou3 and Theocharis C. Stamatatos*,1

1. Department of Chemistry, 1812 Sir Isaac Brock Way, Brock University, L2S 3A1 St. Catharines, Ontario, Canada
2. REQUIMTE-LAQV & Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal
3. Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, USA

10:55 AM
to 11:30 AM
Inorganic Chemistry

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 DyIII and TbIII, 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.