Emily Y. Tsui

A Synthetic Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II

A model compound sheds light on the puzzling role of calcium in the metal cluster that oxidizes water during photosynthesis. Within photosynthetic organisms, the oxygen-evolving complex (OEC) of photosystem II generates dioxygen from water using a catalytic Mn4CaOn cluster (n varies with the mechanism and nature of the intermediate). We report here the rational synthesis of a [Mn3CaO4]6+ cubane that structurally models the trimanganese-calcium–cubane subsite of the OEC. Structural and electrochemical comparison between Mn3CaO4 and a related Mn4O4 cubane alongside characterization of an intermediate calcium-manganese multinuclear complex reveals potential roles of calcium in facilitating high oxidation states at manganese and in the assembly of the biological cluster.

Redox-Inactive Metals Modulate the Reduction Potential in Heterometallic Manganese-Oxido Clusters

Redox-inactive metals are found in biological and heterogeneous water oxidation catalysts, but their roles in catalysis are currently not well understood. A series of high oxidation state tetranuclear-dioxido clusters comprised of three manganese centers and a redox-inactive metal (M) of various charge is reported. Crystallographic studies show an unprecedented Mn3M(μ4-O)(μ2-O) core that remains intact upon changing M or the manganese oxidation state. Electrochemical studies reveal that the reduction potentials span a window of 700 mV, dependent upon the Lewis acidity of the second metal. With the pKa of the redox-inactive metal-aqua complex as a measure of Lewis acidity, these compounds display a linear dependence between reduction potential and acidity with a slope of ca. 100 mV per pKa unit. The Sr2+ and Ca2+ compounds show similar potentials, an observation that correlates with the behavior of the OEC, which is active only in the presence of one of these two metals.

Reactions of a stable monomeric gold(I) hydride complex.

Gold hydride complexes have been postulated as intermediates in a number of homogeneous goldcatalyzed reactions, but relatively little is known about these compounds. The simplest gold hydride, AuH, has been observed in the gas phase and trapped in an inert matrix, but has been extensively studied through theoretical calculations. Complexes with hydride bridges between gold and other metals are well known, but goldonly hydride-bridged complexes have been observed solely in the gas phase. The N-heterocyclic carbene (NHC) ligand IPr (IPr= 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) stabilizes a copper(I) hydride of low nuclearity, dimeric [{(IPr)CuH}2], synthesized from [(IPr)CuCl] in two steps. Since NHC ligands have been shown to effectively support many unusual gold species, we believed the same methodology could yield an analogous gold complex. Herein, we present the structure of a stable gold(I) hydride complex and some of its reactions. The reaction of the known compound [(IPr)AuCl] with sodium tert-butoxide generated [(IPr)AuOtBu] (1), the unsaturated analogue of [(SIPr)AuOtBu] (SIPr= 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene). Treatment of 1 in benzene or dichloromethane with trimethoxysilane yielded [(IPr)AuH] (2) after 1.5 h at room temperature (Scheme 1). A new singlet resonance in the H NMR spectrum, appearing at d= 5.11 ppm (C6D6) or d= 3.38 ppm (CD2Cl2), is assigned as the hydride resonance. This assignment was confirmed through the preparation of the corresponding deuteride complex by reaction of [(IPr)AuCl] with LiDBEt3 [Eq. (1)].

Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals

Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese–oxido cubane clusters [MMn3O4] (M = Sr2+, Zn2+, Sc3+, Y3+) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese–tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese–dioxido clusters. The redox potentials of the [SrMn3O4] and [CaMn3O4] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn3O2] moieties, the present results with more structurally accurate models of the OEC ([MMn3O4]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer.

Modular Functionalization of Carbon Nanotubes and Fullerenes

A series of highly efficient, modular zwitterion-mediated transformations have been developed which enable diverse functionalization of carbon nanotubes (CNTs, both single-walled and multi-walled) and fullerenes. Three functionalization strategies are demonstrated. (1) Trapping the charged zwitterion intermediate with added nucleophiles allows a variety of functional groups to be installed on the fullerenes and carbon nanotubes in a one-pot reaction. (2) Varying the electrophile from dimethyl acetylenedicarboxylate to other disubstituted esters provides CNTs functionalized with chloroethyl, allyl, and propargyl groups, which can further undergo S(N)2 substitution, thiol addition, or 1,3-dipolar cycloaddition reactions. (3) Postfunctionalization transformations on the cyclopentenones (e.g., demethylation and saponification) of the CNTs lead to demethylated or hydrolyzed products, with high solubility in water (1.2 mg/mL for MWCNTs). CNT aqueous dispersions of the latter derivatives are stable for months and have been successfully utilized in preparation of CNT-poly(ethylene oxide) nanocomposite via electrospinning. Large-scale MWCNT (10 g) functionalization has also been demonstrated to show the scalability of the zwitterion reaction. In total we present a detailed account of diverse CNT functionalization under mild conditions (60 degrees C, no strong acids/bases, or high pressure) and with high efficiency (1 functional group per 10 carbon atoms for SWCNTs), which expand the utility of these materials.

Synthetic Cluster Models of Biological and Heterogeneous Manganese Catalysts for O2 Evolution

Artificial photosynthesis has emerged as an important strategy toward clean and renewable fuels. Catalytic oxidation of water to O2 remains a significant challenge in this context. A mechanistic understanding of currently known heterogeneous and biological catalysts at a molecular level is highly desirable for fundamental reasons as well as for the rational design of practical catalysts. This Award Article discusses recent efforts in synthesizing structural models of the oxygen-evolving complex of photosystem II. These structural motifs are also related to heterogeneous mixed-metal oxide catalysts. A stepwise synthetic methodology was developed toward achieving the structural complexity of the targeted active sites. A geometrically restricted multinucleating ligand, but with labile coordination modes, was employed for the synthesis of low-oxidation-state trimetallic species. These precursors were elaborated to site-differentiated tetrametallic complexes in high oxidation states. This methodology has allowed for structure-reactivity studies that have offered insight into the effects of different components of the clusters. Mechanistic aspects of oxygen-atom transfer and incorporation from water have been interrogated. Significantly, a large and systematic effect of redox-inactive metals on the redox properties of these clusters was discovered. With the pKa value of the redox-inactive metal-aqua complex as a measure of the Lewis acidity, structurally analogous clusters display a linear dependence between the reduction potential and acidity; each pKa unit shifts the potential by ca. 90 mV. Implications for the function of the biological and heterogeneous catalysts are discussed.

Oxygen Atom Transfer and Oxidative Water Incorporation in Cuboidal Mn3MOn Complexes Based on Synthetic, Isotopic Labeling, and Computational Studies

The oxygen-evolving complex (OEC) of photosystem II contains a Mn(4)CaO(n) catalytic site, in which reactivity of bridging oxidos is fundamental to OEC function. We synthesized structurally relevant cuboidal Mn(3)MO(n) complexes (M = Mn, Ca, Sc; n = 3,4) to enable mechanistic studies of reactivity and incorporation of μ(3)-oxido moieties. We found that Mn(IV)(3)CaO(4) and Mn(IV)(3)ScO(4) were unreactive toward trimethylphosphine (PMe(3)). In contrast, our Mn(III)(2)Mn(IV)(2)O(4) cubane reacts with this phosphine within minutes to generate a novel Mn(III)(4)O(3) partial cubane plus Me(3)PO. We used quantum mechanics to investigate the reaction paths for oxygen atom transfer to phosphine from Mn(III)(2)Mn(IV)(2)O(4) and Mn(IV)(3)CaO(4). We found that the most favorable reaction path leads to partial detachment of the CH(3)COO(-) ligand, which is energetically feasible only when Mn(III) is present. Experimentally, the lability of metal-bound acetates is greatest for Mn(III)(2)Mn(IV)(2)O(4). These results indicate that even with a strong oxygen atom acceptor, such as PMe(3), the oxygen atom transfer chemistry from Mn(3)MO(4) cubanes is controlled by ligand lability, with the Mn(IV)(3)CaO(4) OEC model being unreactive. The oxidative oxide incorporation into the partial cubane, Mn(III)(4)O(3), was observed experimentally upon treatment with water, base, and oxidizing equivalents. (18)O-labeling experiments provided mechanistic insight into the position of incorporation in the partial cubane structure, consistent with mechanisms involving migration of oxide moieties within the cluster but not consistent with selective incorporation at the site available in the starting species. These results support recent proposals for the mechanism of the OEC, involving oxido migration between distinct positions within the cluster.

Trinucleating Copper: Synthesis and Magnetostructural Characterization of Complexes Supported by a Hexapyridyl 1,3,5‐Triarylbenzene Ligand

Copper threesome: A hexapyridyl ligand based upon a 1,3,5-triphenylbenzene framework coordinates three metal centers in a constrained environment (see picture). The tricopper(I) complex reduces dioxygen to form a tricopper(II) cluster. The capping anions affect the magnetism and EPR spectra of these species and reveal a linear dependence between the antiferromagnetic exchange parameter and the Cu-O-Cu angles.

Redox Potentials of Colloidal n-Type ZnO Nanocrystals: Effects of Confinement, Electron Density, and Fermi-Level Pinning by Aldehyde Hydrogenation.

Electronically doped colloidal semiconductor nanocrystals offer valuable opportunities to probe the new physical and chemical properties imparted by their excess charge carriers. Photodoping is a powerful approach to introducing and controlling free carrier densities within free-standing colloidal semiconductor nanocrystals. Photoreduced (n-type) colloidal ZnO nanocrystals possessing delocalized conduction-band (CB) electrons can be formed by photochemical oxidation of EtOH. Previous studies of this chemistry have demonstrated photochemical electron accumulation, in some cases reaching as many as >100 electrons per ZnO nanocrystal, but in every case examined to date this chemistry maximizes at a well-defined average electron density of ⟨Nmax⟩ ≈ (1.4 ± 0.4) × 10(20) cm(-3). The origins of this maximum have never been identified. Here, we use a solvated redox indicator for in situ determination of reduced ZnO nanocrystal redox potentials. The Fermi levels of various photodoped ZnO nanocrystals possessing on average just one excess CB electron show quantum-confinement effects, as expected, but are >600 meV lower than those of the same ZnO nanocrystals reduced chemically using Cp*2Co, reflecting important differences between their charge-compensating cations. Upon photochemical electron accumulation, the Fermi levels become independent of nanocrystal volume at ⟨N⟩ above ∼2 × 10(19) cm(-3), and maximize at ⟨Nmax⟩ ≈ (1.6 ± 0.3) × 10(20) cm(-3). This maximum is proposed to arise from Fermi-level pinning by the two-electron/two-proton hydrogenation of acetaldehyde, which reverses the EtOH photooxidation reaction.

Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.