Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

The Huisgen 1,3-dipolar cycloaddition reaction of organic azides and alkynes has gained considerable attention in recent years due to the introduction in 2001 of Cu(1) catalysis by Tornoe and Meldal, leading to a major improvement in both rate and regioselectivity of the reaction, as realized independently by the Meldal and the Sharpless laboratories. The great success of the Cu(1) catalyzed reaction is rooted in the fact that it is a virtually quantitative, very robust, insensitive, general, and orthogonal ligation reaction, suitable for even biomolecular ligation and in vivo tagging or as a polymerization reaction for synthesis of long linear polymers. The triazole formed is essentially chemically inert to reactive conditions, e.g. oxidation, reduction, and hydrolysis, and has an intermediate polarity with a dipolar moment of ∼5 D. The basis for the unique properties and rate enhancement for triazole formation under Cu(1) catalysis should be found in the high ∆G of the reaction in combination with the low character of polarity of the dipole of the noncatalyzed thermal reaction, which leads to a considerable activation barrier. In order to understand the reaction in detail, it therefore seems important to spend a moment to consider the structural and mechanistic aspects of the catalysis. The reaction is quite insensitive to reaction conditions as long as Cu(1) is present and may be performed in an aqueous or organic environment both in solution and on solid support.

Cu-catalyzed azide-alkyne cycloaddition.

Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

This review summarizes the use of metal–organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal–organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis

Fascination with supramolecular chemistry over the last few decades has led to the synthesis of an ever-increasing number of elegant and intricate functional structures with sizes that approach nanoscopic dimensions Today, it has grown into a mature field of modern science whose interfaces with many disciplines have provided invaluable opportunities for crossing boundaries both inside and between the fields of chemistry, physics, and biology This chemistry is of continuing interest for synthetic chemists; partly because of the fascinating physical and chemical properties and the complex and varied aesthetically pleasing structures that supramolecules possess For scientists seeking to design novel molecular materials exhibiting unusual sensing, magnetic, optical, and catalytic properties, and for researchers investigating the structure and function of biomolecules, supramolecular chemistry provides limitless possibilities Thus, it transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field

In the early 1960s, the discovery of ‘crown ethers’, ‘cryptands’ and ‘spherands’ by Pedersen,1 Lehn,2 and Cram3 respectively, led to the realization that small, complementary molecules can be made to recognize each other through non-covalent interactions such as hydrogen-bonding, charge-charge, donor-acceptor, π-π, van der Waals, etc Such ‘programmed’ molecules can thus be self-assembled by utilizing these interactions in a definite algorithm to form large supramolecules that have different physicochemical properties than those of the precursor building blocks Typical systems are designed such that the self-assembly process is kinetically reversible; the individual building blocks gradually funnel towards an ensemble that represents the thermodynamic minimum of the system via numerous association and dissociation steps By tuning various reaction parameters, the reaction equilibrium can be shifted towards the desired product As such, self-assembly has a distinct advantage over traditional, stepwise synthetic approaches when accessing large molecules

It is well known that nature has the ability to assemble relatively simple molecular precursors into extremely complex biomolecules, which are vital for life processes Nature’s building blocks possess specific functionalities in configurations that allow them to interact with one another in a deliberate manner Protein folding, nucleic acid assembly and tertiary structure, phospholipid membranes, ribosomes, microtubules, etc are but a selective, representative example of self-assembly in nature that is of critical importance for living organisms Nature makes use of a variety of weak, non-covalent interactions such as hydrogen–bonding, charge–charge, donor–acceptor, π-π, van der Waals, hydrophilic and hydrophobic, etc interactions to achieve these highly complex and often symmetrical architectures In fact, the existence of life is heavily dependent on these phenomena The aforementioned structures provide inspiration for chemists seeking to exploit the ‘weak interactions’ described above to make scaffolds rivaling the complexity of natural systems

The breadth of supramolecular chemistry has progressively increased with the synthesis of numerous unique supramolecules each year Based on the interactions used in the assembly process, supramolecular chemistry can be broadly classified in to three main branches: i) those that utilize H-bonding motifs in the supramolecular architectures, ii) processes that primarily use other non-covalent interactions such as ion-ion, ion-dipole, π–π stacking, cation-π, van der Waals and hydrophobic interactions, and iii) those that employ strong and directional metal-ligand bonds for the assembly process However, as the scale and degree of complexity of desired molecules increases, the assembly of small molecular units into large, discrete supramolecules becomes an increasingly daunting task This has been due in large part to the inability to completely control the directionality of the weak forces employed in the first two classifications above Coordination-driven self-assembly, which defines the third approach, affords a greater control over the rational design of 2D and 3D architectures by capitalizing on the predictable nature of the metal-ligand coordination sphere and ligand lability to encode directionality Thus, this third strategy represents an alternative route to better execute the “bottom-up” synthetic strategy for designing molecules of desired dimensions, ranging from a few cubic angstroms to over a cubic nanometer For instance, a wide array of 2D systems: rhomboids, squares, rectangles, triangles, etc, and 3D systems: trigonal pyramids, trigonal prisms, cubes, cuboctahedra, double squares, adamantanoids, dodecahedra and a variety of other cages have been reported As in nature, inherent preferences for particular geometries and binding motifs are ‘encoded’ in certain molecules depending on the metals and functional groups present; these moieties help to control the way in which the building blocks assemble into well-defined, discrete supramolecules4

Since the early pioneering work by Lehn5 and Sauvage6 on the feasibility and usefulness of coordination-driven self-assembly in the formation of infinite helicates, grids, ladders, racks, knots, rings, catenanes, rotaxanes and related species,7 several groups - Stang,8 Raymond,9 Fujita,10 Mirkin,11 Cotton12 and others13,14 have independently developed and exploited novel coordination-based paradigms for the self-assembly of discrete metallacycles and metallacages with well-defined shapes and sizes In the last decade, the concepts and perspectives of coordination-driven self-assembly have been delineated and summarized in several insightful reviews covering various aspects of coordinationdriven self-assembly15 In the last decade, the use of this synthetic strategy has led to metallacages dubbed as “molecular flasks” by Fujita,16 and Raymond and Bergman,17 which due to their ability to encapsulate guest molecules, allowed for the observation of unique chemical phenomena and unusual reactions which cannot be achieved in the conventional gas, liquid or solid phases Furthermore, these assemblies found applications in supramolecular catalysis18,19 and as nanomaterials as developed by Hupp20 and others21,22

This review focuses on the journey of early coordination-driven self-assembly paradigms to more complex and discrete 2D and 3D supramolecular ensembles over the last decade We begin with a discussion of various approaches that have been developed by different groups to assemble finite supramolecular architectures The subsequent sections contain detailed discussions on the synthesis of discrete 2D and 3D systems, their functionalizations and applications

Supramolecular coordination: self-assembly of finite two- and three-dimensional ensembles.

The tripodal, tetradentate tris(1-(diphenylphosphanyl)-3-methyl-1H-indol-2-yl)phosphane PP3 -ligand 1 stabilizes Ru in the RuII , RuI , and Ru0 oxidation states. The octahedral [(PP3 )RuII (Cl)2 ] (2), distorted trigonal bipyramidal [(PP3 )RuI (Cl)] (3), and trigonal bipyramidal [(PP3 )Ru0 (N2 )] (4) complexes were isolated and characterized by single-crystal X-ray diffraction, NMR, EPR, IR, and ESI-MS. Both open-shell metalloradical RuI complex 3 and the closed-shell Ru0 complex 4 undergo facile (net) abstraction of a Cl atom from dichloromethane, resulting in formation of the corresponding RuII and RuI complexes 2 and 3, respectively.

/pdf/metalloradical-reactivity-of-rui-and-ru0-stabilized-by-an-32n7mtbml8.pdf

Metalloradical Reactivity of RuI and Ru0 Stabilized by an Indole‐Based Tripodal Tetraphosphine Ligand

In [Fe-Fe] hydrogenase mimic systems the ene-1,2-dithiolene ligands play an important role in the stabilisation of the redox-active metal center. This is demonstrated by the benzenedithiolene (bdt) analogue, featuring six terminal carbonyl ligands connected to a di-iron metal center, i.e. [Fe2(bdt)(CO)6]. Here we present a combined experimental and theoretical study that elucidates key intermediates [Fe2(bdt)(CO)6]1- and [Fe2(bdt)(μ-CO)(CO)5]2- in the electrocatalytic production of dihydrogen. A DFT study shows that [Fe2(bdt)(CO)6]1- is the kinetic product after the first one electron reduction, while the previously proposed bridging intermediate species [Fe2(bdt)(μ-CO)(CO)5]1- is kinetically inaccessible. The doubly reduced species [Fe2(bdt)(μ-CO)(CO)5]2- was for the first time structurally characterized using EXAFS. XANES analysis confirms the existence of reduced iron zero species and confirms the distorted geometry that was suggested by the DFT calculations. Combining IR, UV-vis and XAS spectroscopic results with TD-DFT and FEFF calculations enabled us to assign the key-intermediate [Fe2(bdt)(CO)6]2-. This study emphasizes the strengths of combining computational chemistry with advanced spectroscopy techniques.

/pdf/spectroscopic-and-theoretical-investigation-of-the-fe2-bdt-3f09154pc5.pdf

Spectroscopic and theoretical investigation of the [Fe2(bdt)(CO)6] hydrogenase mimic and some catalyst intermediates

We present here the synthesis of chiral BINOL‐derived (BINOL=1,1′‐bi‐2‐naphthol) bisamine and bispyridine‐aldehyde building blocks that can be used for the self‐assembly of novel chiral FeII2L3 cages when mixed with an iron(II) precursor. The properties of a series of chiral cages were studied by NMR and circular dichroism (CD) spectroscopy, cold‐spray ionization MS, and molecular modeling. Upon formation of the M2L3 cages, the iron corners can adopt various isomeric forms: mer, fac‐Δ, or fac‐Λ. We found that the coordination geometry around the metal centers in R‐Cages 1 and 2 were influenced by the chiral BINOL backbone only to a limited extent, as a mixture of cages was formed with fac and mer configurations at the iron corners. However, single cage species (fac‐ RR‐Cage and fac‐ RS‐Cage ) that are enantiopure and highly symmetric were obtained by generating these chiral M2L3 cages by using the bispyridine‐aldehyde building blocks in combination with chiral amine moieties to form pyridylimine ligands for coordination to iron. Next to consistent NMR spectra, the CD spectra confirm the configurations fac‐(Λ,Λ) and fac‐(Δ,Δ) corresponding to RR‐ and RS‐Cage , respectively.

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201801077

Synthesis and Characterization of Self-Assembled Chiral FeII2L3 Cages

Silver(I) induced conformational change in a molecular clip

The development of novel water oxidation catalysts is important in the context of renewable fuels production. Ligand design is one of the key tools to improve the activity and stability of molecular catalysts. The establishment of ligand design rules can facilitate the development of improved molecular catalysts. In this paper it is shown that chemical oxidants can be used to probe oxygen evolution activity for nickel-based systems, and trends are reported that can improve future ligand design. Interestingly, different ligand effects were observed in comparison to other first-row transition metal complexes. For example, nickel complexes with secondary amine donors were more active than with tertiary amine donors, which is the opposite for iron complexes. The incorporation of imine donor groups in a cyclam ligand resulted in the fastest and most durable nickel catalyst of our series, achieving oxygen evolution turnover numbers up to 380 and turnover frequencies up to 68 min-1 in a pH 5.0 acetate buffer using Oxone as oxidant. Initial kinetic experiments with this catalyst revealed a first order in chemical oxidant and a half order in catalyst. This implies a rate-determining oxidation step from a dimeric species that needs to break up to generate the active catalyst. These findings lay the foundation for the rational design of molecular nickel catalysts for water oxidation and highlight that catalyst design rules are not generally applicable for different metals.

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/cssc.202002164

Joost N. H. Reek

Papers

Metalloradical Reactivity of RuI and Ru0 Stabilized by an Indole‐Based Tripodal Tetraphosphine Ligand

Spectroscopic and theoretical investigation of the [Fe2(bdt)(CO)6] hydrogenase mimic and some catalyst intermediates

Synthesis and Characterization of Self-Assembled Chiral FeII2L3 Cages

Silver(I) induced conformational change in a molecular clip

Nickel is a Different Pickle: Trends in Water Oxidation Catalysis for Molecular Nickel Complexes.