Publications

A new pentadentate, redox-active ligand bpy2PYMe has been synthesized and its corresponding transition metal complexes of Fe2+ (1), Co2+ (2), Ni2+ (3), Cu2+ (4), and Zn2+ (5) have been investigated for electro- and photo-catalytic proton reduction in acetonitrile and water, respectively. Under weak acid conditions, the Co complex displays catalytic onset at potentials similar to those of the ligand centered reductions in the absence of acid. Related Co complexes devoid of ligand redox activity catalyze H2 evolution under similar conditions at significantly higher overpotentials, showcasing the beneficial effect of combining ligand-centered redox activity with a redox-active Co center. Furthermore, turnover numbers as high as 1630 could be obtained under aqueous photocatalytic conditions using [Ru(bpy)3]2+ as a photosensitizer. Under those conditions catalytic hydrogen production was solely limited by photosensitizer stability. Introduction of an electron withdrawing CF3 group into the pyridine moiety of the ligand as in bpy2PYMe-CF3 renders its corresponding Co complex 6 less active for proton reduction in electro- and photocatalytic experiments. This surprising effect of ligand substitution was investigated by means of density functional theory calculations which suggest the importance of electronic communication between Co1+ and the redox-active ligand. Taken together, the results provide a path forward in the design of robust molecular catalysts in aqueous media with minimized overpotential by exploiting the synergy between redox-active metal and ligand components.

Building blocks, octahedral (basic zinc acetate units) and triangular (tritopic carboxylic acid), are assembled into a metal-organic framework (MOF-150) having the topology of the FeS2 pyrite net (see picture). Two independent nets interpenetrate, forming the first example of a fully catenated structure with mixed coordination, an occurrence that is ascribed to the self-dual property of the pyrite net (TCA=4,4′,4′′-Tricarboxytriphenylamine).

No abstract is provided for this article.

Carbene polymerization provides polyolefins that cannot be readily prepared from olefin monomers; however, controlled and living carbene polymerization has been a long-standing challenge. Here we report a new class of initiators, (π-allyl)palladium carboxylate dimers, which polymerize ethyl diazoacetate, a carbene precursor in a controlled and quasi-living manner, with nearly quantitative yields, degrees of polymerization >100, molecular weight dispersities 1.2-1.4, and well-defined, diversifiable chain ends. This method also provides block copolycarbenes that undergo microphase segregation. Experimental and theoretical mechanistic analysis supports a new dinuclear mechanism for this process.

To safeguard sensitive user data, web developers typically rely on implicit access-control policies, which they implement using access checks and query filters. This ad hoc approach is error-prone as these scattered checks and filters are easy to misplace or misspecify, and the lack of an explicit policy precludes external access-control enforcement. More critically, it is difficult for humans to discern what policy is embedded in application code and what data the application may access -- an issue that worsens as development teams evolve. This paper tackles policy extraction: the task of extracting the access-control policy embedded in an application by summarizing its data queries. An extracted policy, once vetted for errors, can stand alone as a specification for the application's data access, and can be enforced to ensure compliance as code changes over time. We introduce Ote, a policy extractor for Ruby-on-Rails web applications. Ote uses concolic execution to explore execution paths through the application, generating traces of SQL queries and conditions that trigger them. It then merges and simplifies these traces into a final policy that aligns with the observed behaviors. We applied Ote to three real-world applications and compared extracted policies to handwritten ones, revealing several errors in the latter.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Physisorption in porous materials is a promising route to meet mol. hydrogen (H_2) storage and delivery requirements for
\ntransportation because it is both fast and fully reversible at mild conditions. However, most current candidates have binding
\nenthalpies to H_2 that are too small, which lead to volumetric capacity at 298 K of less than 10 g/L compared to the system
\ntarget of 40 g/L. Using accurate quantum mech. (QM) methods, we det. the H_2 binding enthalpy of 48 compds. (5 linkers and
\n11 different transition metals) used for porous covalent org. frameworks (COF) which we metalated with different transition
\nmetals (TM) , including first row TM (Sc though Cu) and precious TM (Pd and Pt) . We showed that first row TM give similar and
\nsometimes superior van der Waals interactions with H_2 than precious TMs. Based on these results, we constructed 26 new
\nCOFs based on these linkers and we det. the uptake using force fields (FF) based on QM and grand canonical Monte Carlo
\nsimulations. We detd. new COFs that reach the DOE 2017 target of 40 g/L. This work highlights the designing principles for
\nthe optimal interaction enthalpy in the next generation of H_2 storage materials.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Combinatorial approaches together with high-throughput screening have been used to develop highly selective stationary phases for chiral recognition. Libraries of potential chiral selectors have been prepared by the Ugi multicomponent condensation reactions and screened for their enantioselectivity using the reciprocal approach involving a chiral stationary phase with immobilized model target compound N-(3,5-dinitrobenzoyl)-alpha-l-leucine. The best candidates were identified from the library of phenyl amides of 2-oxo-azetidineacetic acid derivatives. This screening also enabled specification of the functionalities of the selector desired to achieve the highest level of chiral recognition. The substituents of the phenyl ring adjacent to the chiral center of the selector candidates exhibited the most profound effect on the chiral recognition. The best candidate was then synthesized on a larger scale, resolved into single enantiomers using preparative enantioselective HPLC, and attached to porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) beads via an ester linkage to afford the desired stationary phase. Selectivities alpha as high as 3.2 were found for the separation of a variety of amino acid derivatives.