Haralampos N. Miras

University of Glasgow | UofG · School of Chemistry

The self-assembly of porous molecular nanocapsules offer unique opportunities to investigate a range of interesting phenomena and applications. However, to design nanocapsules with pre-defined properties, thorough understanding of their structure-property relation is required. Here, we report the self-assembly of two elusive members of the Keplerat...

Molecular metal chalcogenides have attracted great attention as electrocatalysts for the hydrogen evolution reaction (HER). However, efficient utilisation of the active sites and catalytic performance modulation has been challenging. Here we explore the design of immobilized molecular molybdenum polyselenides [Mo2O2S2(Se2)(Sex)]2- that exhibit effi...

The production of hydrogen through water splitting using earth-abundant metal catalysts is a promising pathway for converting solar energy into chemical fuels. However, existing approaches for fine stoichiometric control, structural and catalytic modification of materials by appropriate choice of earth abundant elements are either limited or challe...

Self-assembly has proven a powerful means of preparing structurally intricate nanomaterials, but the mechanism is often masked by the common one-pot mixing procedure. We employed a flow system to study the steps underlying assembly of a previously characterized molybdenum oxide wheel 3.6 nanometers in diameter. We observed crystallization of an int...

Electrospray (ESI) and cryospray mass spectrometry (CSI-MS) are proving to be exceptionally versatile tools when used in conjunction with high resolution time-of-flight (TOF) systems to investigate the self-assembly of supramolecular architectures, inorganic coordination and organometallic compounds, labile molecules and clusters both from a struct...

Based on the strong binding and high selectivity properties of 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-tria-zine (H 2 bihyat) for [U VI O 2 ] 2+ , novel binucleating ligands (BLs) N,N′,N″,N‴-((1,4-phenylenebis(oxy))bis(1,3,5-triazine-6,2,4-triyl))-tetrakis(N-methylhydroxylamine) (H 4 qtn), N 1 ,N 4-bis(4,6-bis(hydroxy-(methyl)amino)-1,3,5-...

The 1,4-reduction of β- and γ-substituted butenolides using 5 mol% of NiCl2.6H2O and NaBH4 in MeOH for rapid access to cis-β,γ-disubstituted γ-butyrolactones is described. The reaction was selective for the cis-product and were obtained in good to excellent yields. This study showcased the influence of sterics and angle strain on the diastereoselec...

The self‐assembly of porous molecular nanocapsules offer unique opportunities to investigate a range of interesting phenomena and applications. However, to design nanocapsules with pre‐defined properties, thorough understanding of their structure‐property relation is required. Here, we report the self‐assembly of two elusive members of the Keplerat...

Efficient separation of water-in-oil emulsion is of great importance but remains highly challenging since such emulsion contains stable tiny droplets with a diameter less than 20 μm. Herein, we reported the fabrication of a modular fibrous functional membrane using an "in situ growth and covalent functionalization" strategy. The as-prepared PAN@LDH...

Hafnium(IV) molecular species have gained increasing attention due to their numerous applications ranging from high-resolution nanolithography, heterogeneous catalysis, and electronics to the design of molecule-based building blocks in metal-organic frameworks (MOFs), with applications in gas separation, sorption, luminescence sensing, and interim...

The design and synthesis of two-dimensional membranes with ultra-high permeability, selectivity, and antifouling properties have been a significant challenge. Herein, we propose a facile approach to design modular polyoxometalate-intercalated layered double hydroxide membranes using a charge-driven self-assembly process. The resultant MgAl-SiW12 me...

Reaction of VIVOCl2 with the nonplanar tetradentate N4 bis-quinoline ligands yielded four oxidovanadium(IV) compounds of the general formula cis-[VIV(O)(Cl)(N4)]Cl. Sequential treatment of the two nonmethylated N4 oxidovanadium(IV) compounds with KF and NaClO4 resulted in the isolation of the species with the general formula cis-[VIV(O)(F)(N4)]ClO4...

A new pyrazole ligand, N,N-bis(2(1',5,5'-trimethyl-1H,1'H-[3,3'-bipyrazol]-1-yl)ethyl)propan-1-amine (L) was synthesized and characterized by 1H-NMR, 13C-NMR, FT-IR and HRMS. The coordination ability of the ligand has been employed for the construction of a new family of coordination complexes, namely: [Cu2LCl4] (1), [ML(CH3OH)(H2O)](ClO4)2 (MII =...

Despite the proliferation of tungstate and molybdate polyoxometalates (POMs) the inclusion of sulfides into these structures proved to be challenging. The use of appropriate preformed thiomolybdate building blocks has over recent years developed into an extensive field with a wide range of diverse structural features and sizes. Initial explorations...

Thermal insulation materials show a substantial impact on civil and military fields for applications. Fabrication of efficient, flexible, and comfortable composite materials for thermal insulation is thereby of significance. Herein, a "fiber templated epitaxial growth" strategy was adopted to construct PAN@LDH (PAN = polyacrylonitrile; LDH = layere...

The hydrolytically stable dioxime ligand (2Ζ-6Ζ)-piperidine-2,6-dione (H3pidiox), acts as a strong chelator mainly with hard metals in high oxidation states, a pre-requisite for potential applications in metal sequestering processes from...

The term self-assembly is used to describe the formation of many molecules and supramolecular architectures, but often, the precise mechanism is neglected. Here, we have investigated the kinetics of the self-assembly of the simplest heteropolyoxoanion, the Keggin ion [XMo12O40]x–. This study used variable temperature UV/vis spectroscopy to show tha...

The siderophore organic ligand N,2-dihydroxybenzamide (H2dihybe) incorporates the hydroxamate group, in addition to the phenoxy group in the ortho-position and reveals a very rich coordination chemistry with potential applications in medicine, materials, and physical sciences. The reaction of H2dihybe with TiCl4 in methyl alcohol and KOH yielded th...

A [Mo7O24]6‐ polyanion is used to catalyze the hydrolysis of a phosphoester bond, although the polyanion is not directly responsible for the catalysis. The real catalyst is produced in situ of the reaction media through the decomposition of the initial polyoxometalate leading to the [Mo2O8H4] dimeric species, which is the real catalytic species. Fo...

Water oxidation plays a crucial role in both natural and artificial photosynthesis, which is an attractive solution to the depletion of fossil fuels as energy sources due to the increasing consumption. Thus, the search for oxygen evolution reaction catalysts is a hot topic of research. Reaction of the N5-tripodal amidate ligand, N-{2-[(bis(pyridine...

Phosphoester hydrolysis is an important chemical step in DNA repair. One archetypal molecular model of phosphoesters is para‐nitrophenylphosphate (pNPP). It has been shown previously that the presence of molecular metal oxide [Mo 7 O 24 ] 6– may catalyse the hydrolysis of pNPP through the partial decomposition of polyoxomolybdate framework resultin...

Alzheimer's disease (AD) is a neurodegenerative disorder of the central nervous system. The main pathophysiological mechanisms involve cholinergic neurotransmission, beta-amyloid (Αβ) and Tau proteins, several metal ions and oxidative stress, among others. Current drugs offer only relief of symptoms and not a cure of AD. Accumulating evidence sugge...

A new flexible bis-pyrazol-bis-acetate ligand, diethyl 2,2’-(pyridine-2,6-diylbis (5-methyl-1H-pyrazole-3,1-diyl))diacetate (L), has been synthesised, and three coordination complexes, namely, [Zn(L)2](BF4)2 (1), [MnLCl2] (2) and [CdLCl2] (3) have been obtained. All ligands and complexes were characterised by IR, mass spectroscopy, thermogravimetri...

Two-dimensional organic-inorganic hybrid materials based on layered double hydroxides (LDHs) have drawn significant attention during the last decade. The development of such materials is usually based on the intercalation of LDHs. However, the direct intercalation of organic guest molecules into the gallery of LDHs using carbonate-intercalated LDHs...

div>Phosphoester hydrolysis is an important chemical step in DNA repair. One archetypal molecular model of phosphoesters is para-nitrophenylphosphate (pNPP). It has been shown previously that the presence of molecular metal oxide [Mo7O24]6– may catalyse the hydrolysis of pNPP through the partial decomposition of polyoxomolybdate framework resulting...

The chelating catechol/oxime ligand 2,3-dihydroxybenzaldehyde oxime (H3dihybo) has been used to synthesize one titanium(IV) and two zirconium(IV) compounds that have been characterized by single-crystal X-ray diffraction and 1H and 13C NMR, solid-state UV-vis, and ESI-MS spectroscopy. The reaction of TiCl4 with H3dihybo and KOH in methanol, at ambi...

The chiral dicobalt(II) complex [Co II 2 (μ 2-L) 2 ] (1) (H 2 L = N 2 ,N 6-di(quinolin-8-yl)pyridine-2,6-dicarboxamide) and its tert-butyl analogue [Co II 2 (μ 2-L Bu) 2 ] (2) were synthesized and structurally characterized. Addition of one equivalent of AgSbF 6 to the dichloromethane solution of 1 and 2 resulted in the isolation of the mixed-valen...

Understanding magnetic anisotropy and specifically how to tailor it is crucial in the search for high-temperature single-ion magnets. Herein, we investigate the magnetic anisotropy in a six-coordinated cobalt(II) compound that has a complex geometry and distinct triaxial magnetic anisotropy from the perspective of the electronic structure, using el...

Here we show how a simple inorganic salt can spontaneously form autocatalytic sets of replicating inorganic molecules that work via molecular recognition based on the {PMo 12 } ≡ [PMo 12 O 40 ] 3– Keggin ion, and {Mo 36 } ≡ [H 3 Mo 57 M 6 (NO) 6 O 183 (H 2 O) 18 ] 22– cluster. These small clusters are able to catalyze their own formation via an aut...

The energetically viable fabrication of stable and highly efficient solid acid catalysts is one of the key steps in the large‐scale transformation processes of biomass resources. Herein, we report the covalent modification of the classical Dawson polyoxometalate (POMs) with sulphonic acids (‒SO3H) by grafting the sulfonic acid groups on the POM’s s...

Cellulose acetate propionate (CAP), a high value-added chemical, is traditionally prepared using H2SO4 as catalyst. Replacement of the mineral acids by solid acids is current research focus for green and sustainable production of CAP. Herein, we reported the fabrication of novel solid acid catalyst HPW/Si(Et)Si-Dim-SO3H (Si(Et)Si = ethyl-bridged or...

Over the last decades, the field of polyoxometalate (POM) chemistry has advanced rapidly at its frontiers, especially where interdisciplinary research efforts diffused the boundaries of well-defined disciplines such as materials science, physics and environmental chemistry. These efforts were reflected by fascinating discoveries ranging from extrem...

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

The electrochemical generation of hydrogen is a key enabling technology for the production of sustainable fuels. Transition metal chalcogenides show considerable promise as catalysts for this reaction, but to date there are very few reports of tellurides in this context, and none of these transition metal telluride catalysts are especially active....

In recent years, great attention has been paid to cascade reactions, which can improve efficiency and reduce waste production by implementing several consecutive reactions. Herein, two bifunctional catalysts were successfully prepared by precise control of the oriented layered double hydroxides (LDHs) growth on graphene oxides (GO) using a single‐d...

Biological self-replication is driven by complex machinery requiring large amounts of sequence information too complex to have formed spontaneously. This presents a fundamental problem for understanding the origins self-replication and by extension, life. One route for the emergence of self-replicators is via autocatalytic sets, but experimentally...

Biological self-replication is driven by complex machinery requiring large amounts of sequence information too complex to have formed spontaneously. This presents a fundamental problem for understanding the origins self-replication and by extension, life. One route for the emergence of self-replicators is via autocatalytic sets, but experimentally...

Polyoxometalates (POMs) are very versatile molecules and can thus be finely tuned in order to interact with biomolecules and possibly catalyse relevant biochemical reactions. One of the most important examples of such interactions is the reported anti-tumour activity of [Mo7O24]6-. In 2008 was demonstrated the ability of this POM species to catalys...

The production of hydrogen through water splitting using earth-abundant metal catalysts is a promising pathway for converting solar energy into chemical fuels. However, existing approaches for fine stoichiometric control, structural and catalytic modification of materials by appropriate choice of earth abundant elements are either limited or challe...

Traditionally, chemists have relied on years of training and accumulated experience in order to discov-er new molecules. But the space of possible molecules so vast, only a limited exploration with the tra-ditional methods can be ever possible. This means that many opportunities for the discovery of inter-esting phenomena have been missed, and in a...

As a biomass‐derived platform molecule, 5‐hydroxymethylfurfural (5‐HMF) is a highly desirable feedstock for the manufacturing of high value‐added chemicals ranging from starting materials for polyesters to biofuels. In this work, we reported the fabrication of a series of multicomponent solid acid catalysts based on heteropolyacids immobilized ILs‐...

In this work, we explore the implementation of new design principles for the development of efficient molecular HER catalysts. We aim to investigate the effects of stoichiometric and structural control resulting from the appropriate choice of the chalcogen elements and their ratio (e.g. O 2− /S 2 2− , O 2− /S 2 2− /S 4 2−) within the coordination s...

Polyoxometalates (POMs) have been found to be good end-capping ligands for gold nanoparticles (AuNPs). Herein, we introduce a new synthetic method to synthesize gold nanoparticle-POM hybrids by heating a solution of AuNO3(PMe3) in acetonitrile in the presence of appropriate POM species with tetrabutylammonium (TBA) as a countercation at 120 °C in a...

Heterometallic rare earth transition metal compounds of dithioxalate (dto)2–, [Ni{(dto)LnTp2}2] (Ln= Y (1), Gd (2); Tp = hydrotris(pyrazol-1-yl)borate) were synthesised. The Lewis acidic rare earth ions are bound to the dioxolene and chemical reduction of 1 and 2 with cobaltocene yielded [CoCp2]+[Ni{(dto)LnTp2}2]–• Ln = Y (3), Gd (4). The reduction...

Reaction of the cyclic ligand (2Z,6Z)-piperidine-2,6-dione dioxime with TiCl4 and KOH yielded the hexanuclear cluster K6{Ti6IV(μ3-Ο)2(μ-Ο)3(CH3O)6[μ2-η1,η1,η2-Hpidiox -O,N,O')]4[μ2-η1,η1,η2-pidiox -O,N,O')]2}.7.5CH3OH possessing a new {Ti6O5} structural motif. The cluster core {Ti6O5} is wrapped by external tripodal imide dioxime ligands, showing g...

div> Traditionally, chemists have relied on years of training and accumulated experience in order to discover new molecules. But the space of possible molecules so vast, only a limited exploration with the traditional methods can be ever possible. This means that many opportunities for the discovery of interesting phenomena have been missed, and i...

Cellulose esters are cellulose derivatives with broad application in plastics, films, fibers, coatings, textiles industries etc. Taking cellulose acetate propionate (CAP) as an example, high viscosity CAP products are widely used in printing inks, hot-melt dip coatings and lacquer coatings etc. However, it was and remains to be a great challenge to...

Molybdenum oxy-sulfides provide the latest molecular resource to assist the hydrogen reduction reaction.

The production of hydrogen through water splitting using earth-abundant metal catalysts is a promising pathway for converting solar energy into chemical fuels. However, existing approaches for fine stoichiometric control, structural and catalytic modification of materials by appropriate choice of earth abundant elements are either limited or challe...

A bis(dithiolene)gold complex is presented as a model for an organic molecular electron spin qubit attached to a metallic surface that acts as a conduit to electrically address the qubit. A two-membered electron transfer series is developed of the formula [AuIII(adt)2]1–/0, where adt is redox-active dithiolene ligand that is sequentially oxidized a...

The activation of dioxygen by metal ions is critical in chemical and bio-chemical processes. A scientific challenge is the elucidation of the activation site of dioxygen, in some copper metalloproteins, which is either the metal center or the substrate. In an effort to address this challenge, we prepared a series of new copper(II) complexes (1.2H2O...

The intrinsic redox activity of the dithiolene ligand is presented here as the novel spin host in the design of prototype molecular electron spin qubit where the traditional roles of the metal and ligand components in coordination complexes are inverted. A series of paramagnetic bis(dithiolene) complexes with group 10 metals – nickel, palladium, pl...

Correction for ‘Polyoxometalate based open-frameworks (POM-OFs)’ by Haralampos N. Miras et al. , Chem. Soc. Rev. , 2014, 43 , 5679–5699.

The catalytic aminolysis of epoxides can lead to a large number of β‐amino alcohols which are of particular interest in industrial applications. In this paper, we demonstrate for the first time the use of a polyoxometalate [CoW12O40]5‐ intercalated layered double hydroxides (Zn3Al‐LDH) material as an efficient solid acid catalyst for the catalytic...

Utilizing new experimental approaches and gradual understanding of the underlying chemical processes has led to advances in the self-assembly of inorganic and metal–organic compounds at a very fast pace over the last decades. Exploitation of unveiled information originating from initial experimental observations has sparked the development of new f...

Although directly relevant to metal mediated biological nitrification and the coordination chemistry of peroxide, the transition metal complexes of hydroxylamines and their functionalized variants remain mainly unexplored except vanadium(V) and molybdenum(VI). Reaction of the chelating hydroxylamine ligand 3,3′-(hydroxyazanediyl)dipropanamide (Hhyd...

Direct solar-to-hydrogen conversion can be achieved via photoelectrochemical water splitting, and is an attractive approach for the storage of sunlight as a chemical fuel. ¹ However, current technologies rely on expensive components such as the noble metal platinum electrocatalyst, making such devices economically inviable. Efforts have therefore r...

Utilization of [Mo2S2O2(H2O)6]2+ and tellurite anion, led to the formation of three new clusters, 1-3, with unique structural features. The tellurite anion not only templated the formation of [(Mo2O2S2)4(TeO3)(OH)9]3- 1...

Mixed-valent polyoxometalate (POM) clusters are one of the most interesting host species showing a wide range of structural features and properties. We report the facile preparation and functionalization of a mixed-valent polyoxofluorovanadates where two electrons are trapped to antipodal sites of the clusters. The first members of this family of c...

Mixed valence/metal polyoxometalate (POM) clusters are one of the most interesting host species showing the ability to incorporate a wide range of heteroatoms of various charges and geometries. We report herein, the incorporation of different pyramidal EO32- heteroanions (E = PH, S, Se, Te) which are responsible not only for directing the templated...

The Cover Feature shows the efficient catalytic conversion of sulphides and olefins under mild conditions using a polyoxometalate based multicomponent composite material. In their Full Paper, T. Li, W. Zhang et al. exploited the cooperative effects introduced by the various components of the composite material to design a flexible and stable multif...

Development of inexpensive and robust electrocatalysts towards oxygen reduction reaction (ORR) is crucial for the cost-affordable manufacturing of metal-air batteries and fuel cells. Here we show that cross-linked CoMoO4 nanosheets and reduced graphene oxide (CoMoO4/rGO) can be integrated in a hybrid material under one-pot hydrothermal conditions,...

In recent years, great attention has been dedicated to the development of heterogeneous base catalysts rendering green and sustainable process in benign aqueous media. Herein, the ionic liquids modified layered double hydroxides (LDHs) based catalysts of LDH-ILs-Cn (n = 4, 8, 12) were prepared by adopting an exfoliation/assembly strategy, in which...

Layered double hydroxides (LDHs) are an important large class of two-dimensional (2D) anionic lamellar materials that possess flexible modular structure, facile exchangeability of inter-lamellar guest anions and uniform distribution of metal cations in the layer. Owing to the modular accessible gallery and unique inter-lamellar chemical environment...