Solvent-controlled ion-coupled charge transport in microporous metal chalcogenides

Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials. These interactions may strongly influence the electronic behavior of microporous materials that confine ions and charges to length scales comparable to proton-coupled electron transfer. Yet despite mounting evidence that both solvent and electrolyte influence charge transport through ion–charge interactions in metal–organic frameworks, fundamental microscopic insights are only just beginning to emerge. Here, through electrochemical analysis of two open-framework chalcogenides TMA₂FeGe₄S₁₀ and TMA₂ZnGe₄S₁₀, we outline the key signatures of ion-coupled charge transport in band-type and hopping-type microporous conductors. Pressed-pellet direct-current and impedance techniques reveal that solvent enhances the conductivity of both materials, but for distinct mechanistic reasons. This analysis required the development of a fitting method that provides a novel quantitative metric of concerted ion–charge motion. Taken together, these results provide chemical parameters for a general understanding of electrochemistry in nanoconfined spaces and for designing microporous conductors and electrochemical methods used to evaluate them.

Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials.     

LNA functionalized gold nanoparticles as probes for double stranded DNA through triplex formation

Nanoparticle modified LNA probes have been used for colorimetric identification of double stranded DNA via parallel triplex formation, eliminating the need for prior denaturation of the target duplex.     

Porphyrin/Platinum(II) C^N^N Acetylide Complexes: Synthesis,Photophysical Properties,and Singlet Oxygen Generation

A new class of substituted porphyrins has been developed in which a different number of cyclometalated Pt^II C^N^N acetylides and polyethylene glycol (PEG) chains are attached to the meso positions of the porphyrin core, which are meant for photophysical, electrochemical, and in vitro light‐induced singlet oxygen (¹O₂) generation studies. All of these Zn^II porphyrin–Pt^II C^N^N acetylide conjugates show moderate to high (Φ_Δ=0.55 to 0.63) singlet oxygen generation efficiency. The complexes are soluble in organic solvents but, despite the PEG substituents, slowly aggregate in aqueous solvent systems. These conjugates also exhibit interesting photophysical properties, including near‐complete photoinduced energy transfer (PEnT) through the rigid acetylenic bond(s) from the Pt^II C^N^N antenna units to the Zn^II porphyrin core, which shows sensitized luminescence, as shown by quenching of Pt^II C^N^N‐based luminescence. Electrochemical measurements show a set of redox processes that are approximately the sum of what is observed for the Pt^II C^N^N acetylide and Zn^II porphyrin units. UV/Vis spectroscopic properties are supported by DFT calculations.     

Protein immobilization capacity and covalent binding coverage of pulsed plasma polymer surfaces

Three carbon surfaces were deposited using pulsed plasma enhanced chemical vapour deposition method: a low and a high nitrogen-containing plasma polymer surfaces and a diamond-like carbon surface. The surfaces were analysed using both X-ray photoelectron spectroscopy (XPS) technique and the enzyme-linked immunosorbent assay (ELISA) method combining with sodium dodecyl sulphate (SDS) cleaning to investigate the capacity and covalent binding of the immobilized proteins. A good correlation was found on quantification of remaining protein after SDS cleaning using the ELISA method and the XPS technique. All surfaces had similar initial capacity of protein attachment but with large different resistance to SDS cleaning. The analysis showed that the high nitrogen-containing plasma polymer was the best biocompatible material due to its highest resistance to SDS cleaning, i.e. with the highest quantity (∼80%) of proteins bound covalently.     

Definability in Substructure Orderings,II: Finite Ordered Sets

Let \({{\uppercase {\mathcal{p}}}} \) be the ordered set of isomorphism types of finite ordered sets (posets), where the ordering is by embeddability. We study first-order definability in this ordered set. We prove among other things that for every finite poset P, the set \(\{p,p^{\partial}\}\) is definable, where p and \(p^{\partial}\) are the isomorphism types of P and its dual poset. We prove that the only non-identity automorphism of \({{\uppercase {\mathcal{p}}}}\) is the duality map. Then we apply these results to investigate definability in the closely related lattice of universal classes of posets. We prove that this lattice has only one non-identity automorphism, the duality map; that the set of finitely generated and also the set of finitely axiomatizable universal classes are definable subsets of the lattice; and that for each member K of either of these two definable subsets, \(\{K,K^{\partial}\}\) is a definable subset of the lattice. Next, making fuller use of the techniques developed to establish these results, we go on to show that every isomorphism-invariant relation between finite posets that is definable in a certain strongly enriched second-order language \(\textup{\emph L}_2\) is, after factoring by isomorphism, first-order definable up to duality in the ordered set \({{\uppercase {\mathcal{p}}}}\). The language \(\textup{\emph L}_2\) has different types of quantifiable variables that range, respectively, over finite posets, their elements and order-relation, and over arbitrary subsets of posets, functions between two posets, subsets of products of finitely many posets (heteregenous relations), and can make reference to order relations between elements, the application of a function to an element, and the membership of a tuple of elements in a relation.     

DFT study of paramagnetic adducts of tris-(8-hydroxyquinoline)aluminum (III)

Radicals formed by the addition of hydrogen (H) or muonium (Mu) to tris(8-hydroxyquinoline)aluminum(III) (Alq(3)) have been studied using density functional theory (DFT) calculations. Drew et al. (Phys. Rev. Lett. 2008, 100, 116601) studied Alq(3) using the longitudinal field muon spin relaxation technique and assumed the formation of muoniated radicals and rapid intermolecular electron hopping with a rate of (1.4 ± 0.2) × 10(12) s(-1). In this work, the results of DFT calculations on Alq(3), the H/Mu adducts of Alq(3), and the corresponding anions and cations are reported. The energy required to transfer an electron to or from the H/Mu adducts of Alq(3) is prohibitively large, ranging from 4.09 to 5.68 eV, which suggests that the unpaired electron does not hop onto neighboring molecules and that there is no long-range diffusion of the unpaired electron. The hyperfine coupling constants for the muoniated radicals were calculated and used to predict avoided level crossing resonance fields, which will allow experimenters to confirm that the unpaired electron is localized in close proximity to the muon.     

Self-assembled monolayer of a peroxo-bridged dinuclear cobalt(III) complex on Au(111)

Densely packed Self-Assembled Monolayers (SAMs) of a peroxide-bridged dicobalt complex, [Co2(O2)(bpbp)(O2CCH2CH2S)]2+, 3, (bpbp- = 2,6-bis((N,N-bis-(2-picolyl)amino)-methyl)-4-tert-butylphenolato) have been prepared on atomically planar Au(111) surfaces. Surface voltammetric and interfacial capacitance data, along with electrochemical scanning tunnelling microscopy (in situ STM) imaging, support the formation of a densely packed adlayer of 3 attached via a gold-thiolate bond. In solution, the disulfide linked precursor for 3 reversibly binds dioxygen with high affinity. Electrochemical measurements show that the redox potential of the O22-/O2*- couple of the monolayer of 3 is cathodically shifted by nearly 500 mV compared to the precursor in solution. This is attributed to the close proximity of the O2 binding site to the gold surface. Since the redox potential of the O22-/O2*- couple reflects tentatively the binding affinity of O2 to the deoxygenated CoII2 binding site, the potential of the O22-/O2*- couple of the SAM of 3 suggests a much higher affinity towards O2 compared to the solution precursor.     

Phosphine dissociation and diffusion on Si(001) observed at the atomic scale

A detailed atomic-resolution scanning tunneling microscopy (STM) and density functional theory study of the adsorption, dissociation, and surface diffusion of phosphine (PH(3)) on Si(001) is presented. Adsorbate coverages from approximately 0.01 monolayer to saturation are investigated, and adsorption is performed at room temperature and 120 K. It is shown that PH(3) dissociates upon adsorption to Si(001) at room temperature to produce both PH(2) + H and PH + 2H. These appear in atomic-resolution STM images as features asymmetric-about and centered-upon the dimer rows, respectively. The ratio of PH(2) to PH is a function of both dose rate and temperature, and the dissociation of PH(2) to PH occurs on a time scale of minutes at room temperature. Time-resolved in situ STM observations of these adsorbates show the surface diffusion of PH(2) adsorbates (mediated by its lone pair electrons) and the dissociation of PH(2) to PH. The surface diffusion of PH(2) results in the formation of hemihydride dimers on low-dosed Si(001) surfaces and the ordering of PH molecules along dimer rows at saturation coverages. The observations presented here have important implications for the fabrication of atomic-scale P dopant structures in Si, and the methodology is applicable to other emerging areas of nanotechnology, such as molecular electronics, where unambiguous molecular identification using STM is necessary.     

NO Reactions Inside Crystals

Reactions of chemisorbed reagents inside the crystalline molecular solid state are rare but offer unexploited methods for selective solvent-free chemical synthesis. Here we show that the greenhouse gas precursor, nitric oxide (NO) is chemisorbed by crystals of the hexafluorophosphate salts of complexes containing dicobalt sites. On NO sorption a cascade of reactions results in the in-crystal synthesis of nitrite and other gaseous NO_x. Recrystallization enabled structural elucidation of the mixed valent {[(bpbp)Co₂(μ-(η¹-O : η¹-N)-ONO)]₂(bdc)}⁴⁺ (bpbp=2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato, bdc=1,4-benzenedicarboxylato) cation. Overlapping signals in the solid-state EPR spectra confirm the Co^IICo^III oxidation state and the presence of NO₂ trapped inside the unrecrystallised solid products (br. g=4, triplet g=2 (340 mT), A(N)=73 MHz), despite three cycles of vacuum and N₂ flushing. Consistently, ν_N−O bands appear in the Raman and IR spectra that are due to the coordinated nitrate and the trapped NO₂ that were synthesized in-crystal. The latter is expelled by heating the solid to 160 °C or by recrystallization. Dimetallic cooperativity is proposed for the NO transformations in these rare examples of selective, chemisorptive substrate reactions in the solid-state.