Browsing by Subject "Inorganic"

Now showing 1 - 4 of 4

Selective anion exchange and anion-tuned gas sorption in a phosphine coordination material
(2019-05-06) Riparetti, Ryan Douglas; Humphrey, Simon M.
Herein we report a new ligand tris(4-(pyrid-4-yl)phenyl)phosphine sulfide (tppps) as a building block for the synthesis of a zeolite-like Phosphine Coordination Material (PCM). PCM-63 was made solvothermally with tppps and AgNO₃, producing off-white prisms. The material underwent selective anion exchange with PF₆ ̄ and ClO₄ ̄ over five other anions in a competition experiment. PCM-63 could remove 36.4% and 27.0% of 1 mM ReO₄ ̄ and ClO₄ ̄ in the presence of 100 mM Cl ̄, respectively. Four single-crystal to single-crystal studies were carried out with ReO₄ ̄, PF₆ ̄, ClO₄ ̄, and BF₄ ̄, each showing numerous CH···X (X = O, F) interactions between the framework and the anion. The anion-exchanged materials exhibited a large increase in surface areas for gases. Most notably, PCM-63-BF₄ and PCM-63-PF₆ exhibited a CO₂ surface area of 463 m²g⁻¹ and 466 m²g⁻¹, respectively. This is a large increase in surface area from PCM-63, which has a CO₂ surface area of 80 m²g⁻¹, suggesting that CH···F interactions stabilize the framework
Synthesis and Characterization of Luminescent Lanthanide Nano-Rings
(2016) Bard, Alexander; Jones, Richard
It is not uncommon for inorganic chemistry classes to gloss over the chemistry of the lanthanides. Because most inorganic chemists work closely with the d -electrons of the transition metals, the shielded and inert f -electrons of the lanthanides may at first glance seem monotone or even boring. However, to truly appreciate the lanthanides and the complexes they produce, one must come to embrace their chemical simplicity and understand their much more interesting electronic properties that lead to extremely interesting luminescent and magnetic molecules. Furthermore, though the lanthanides generally only form 3+ ions, it is important to consider that their high coordination number can lead to some very large and unusual molecular structures. Additionally, lanthanide complexes are known for their photophysical properties, specifi cally their sharp emission peaks. This, along with the fact that they don't photobleach and are relatively nontoxic, make them ideal for biological probes. If the ligand in the complex can be functionalized to couple with an antibody, the complex should then be able to follow the antibody wherever it goes, for example, to a cancerous tumor, and the probes would then aggregate in the area, causing localized luminescence, aiding in early detection of cancer. This thesis reports the synthesis of a 42-nuclear lanthanide nano-ring: likely the highest nuclearity lanthanide complex ever produced. This complex, referred to as Ln 42, is produced by reacting an ortho-vanillin based ligand with lanthanide acetate, the suitable lanthanides being gadolinium, terbium, dysprosium, and holmium. The complex self-assembles, interestingly, fi rst hydrolyzing the ligand such that the only portion that remains in the final complex is deprotonated ortho-vanillin. Acetate and hydroxyl groups also remain in the final complex, in addition to the lanthanide centers. The structure in the crystalline solid state was determined using single crystal X-ray diffraction.
Synthesis and characterization of n-heterocyclic phosphenium and arsenium salts
(2011-05) Hoberg, Clint R.; Cowley, Alan H.; Holliday, Bradley J
Two ligand types were employed for the one-step preparations of heavy group 15 cations, namely, diazabutadiene (DAB) and bis(imino)acenaphthene (BIAN). By exploiting the redox properties of these ligands, in conjunction with two different synthetic strategies, it was possible to synthesize a variety of phosphenium and arsenium salts in relatively high yields. The first synthetic method took advantage of the known equilibrium between PI/PI3 in solution. The second synthetic route employed SnCl2 as the reducing agent for converting the reactive trihalides ECl3 into the corresponding “ECl” moieties (E = P, As).
The assembly of inorganic nanocrystals using dynamic covalent chemistry
(2022-05) Dominguez, Manuel Nicholas; Milliron, Delia (Delia Jane); Truskett, Thomas M; Anslyn, Eric V; Rose, Michael
Here I show the work accomplished in my graduate career on metal oxide nanocrystals and their assembly into unique gels. Nanocrystals were synthesized using a well-established method that was adapted to improve subsequent functionalization. Collaborations between the Anslyn group led to ligands that were designed for tunable orthogonal covalent linkages between particles. Establishing a well solid foundation for controllable assembly through this collaboration was the goal, along with a better understanding of the system through collaboration with the Truskett lab and the work they do on simulations and theory. Applying what was learned and theorized into studying differences in similar systems for changes to the optical response also became a goal of the work presented. All put together an understanding of the building blocks of assembly, the assembly method, and finally the properties of the assembly are discussed within.