
Floriana Tuna- The University of Manchester
Floriana Tuna
- The University of Manchester
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Publications (408)
Although two examples of σ-bonded trans-bent [RSbSbR]•– (R = bulky organo- or Ga-groups) that formally contain the Sb2•3– radical trianion moiety are known in p-block chemistry, d- or f-element Sb2•3– radical trianion complexes, with or without R-substituents, have remained elusive. Here, we report that reduction of a 77:23 mix of [{Th(TrenTIPS)}2(...
Doped colloidal quantum dots (CQDs) are promising spin-photon interfaces, combining excellent optical properties and a substrate-free, nano-positionable platform. Here, we report the synthesis of InP/ZnSeS core-shell CQDs from zinc sulphide...
Two new 2p–3d complexes, (Et3NH)[ML(hfac)2], have been obtained using the nitronyl-nitroxide radical (HL) derived from 2-hydroxy-3-methoxy-5-nitrobenzaldehyde (M = Mn 1; Co 2). The two compounds are isomorphous and their structures consist of anionic mononuclear species, [M(hfac)2L]−, M = Mn 1; Co 2, and triethylammonium cations, Et3NH+. The metal...
Phenylacetylene is a detrimental impurity in the polymerisation of styrene, capable of poisoning catalysts even at ppm levels and significantly degrading the quality of polystyrene. The semi-hydrogenation of phenylacetylene to...
A new calcium-based Room temperature Stable Electride (RoSE), K[{Ca[N(Mes)(SiMe3)]3(e–)}2K3] (2), is successfully synthesized from the reaction of a calcium tris-amide, [Ca{N(Mes)(SiMe3)}3K] (1) (Mes = 2,4,6-trimethylphenyl), with potassium under mechanochemical treatment. The dimeric structure of K[{Ca[N(Mes)(SiMe3)]3(e–)}2K3] is calculated using...
High NH 3 uptake is observed in a series of paddlewheel [Cu 2 (O 2 CR) 4 ] metal–organic frameworks.
Reactions between [(TrenTIPS)UVIN] (1, TrenTIPS = {N(CH2CH2NSiPri3)3}3) and [MII(5-C5R5)2] (M/R = Cr/H, Mn/H, Fe/H, Ni/H) were intractable, but M/R = Co/H or Co/Me afforded [(TrenTIPS)UV=N-(1:4-C5H5)CoI(5-C5H5)] (2) and [(TrenTIPS)UIV-NH2] (3), respectively....
In this work, a polyhedral silsesquioxane (POSS) was used as an engineered drug delivery system for two oxindolimine-copper(II) anticancer complexes, [Cu(isaepy)]+ and [Cu(isapn)]+. The interest in hybrid POSS comes from...
A new calcium-based Room temperature Stable Electride (RoSE), K[{Ca[N(Mes)(SiMe 3 )] 3 ( e – )} 2 K 3 ] (2), is successfully synthesized from the reaction of a calcium tris-amide, [Ca{N(Mes)(SiMe 3 )} 3 K] (1) (Mes = 2,4,6-trimethylphenyl), with potassium under mechanochemical treatment. The dimeric structure of K[{Ca[N(Mes)(SiMe 3 )] 3 ( e – )} 2...
The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemica...
We introduce the boryloxide ligand {(HCNDipp)2BO}⁻ (NBODipp, Dipp = 2,6-di-isopropylphenyl) to actinide chemistry. Protonolysis of [U{N(SiMe3)2}3] with 3 equiv of NBODippH produced the uranium(III) tris(boryloxide) complex [U(NBODipp)3] (1). In contrast, treatment of UCl4 with 3 equiv of NBODippK in THF at room temperature or reflux conditions prod...
We examine lanthanide (Ln)–ligand bonding in a family of early Ln³⁺ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin...
MFM‐520(Zn) confines dimers of NO2 with a high adsorption of 4.52 mmol g⁻¹ at 1 bar at 298 K. The synthesis and the incommensurate structure of Cu‐doped MFM‐520(Zn) are reported. The introduction of paramagnetic Cu²⁺ sites allows investigation of the electronic and geometric structure of metal site by in situ electron paramagnetic resonance (EPR) s...
Deuterium labelling of organic compounds is an important process in chemistry. We report the first example of photocatalytic dehalogenative deuteration of both arylhalides and alkylhalides (40 substrates) over a metal–organic framework, MFM‐300(Cr), using CD3CN as the deuterium source at room temperature. MFM‐300(Cr) catalyses high deuterium incorp...
We report the synthesis of a series of temperature‐sensitive non‐classical early Ln(II) (Ln=lanthanide) complexes, [K(2.2.2‐cryptand)][Ln(Cptt)3] (Cptt=C5H3tBu2‐1,3; 1‐Ln; Ln=La−Nd). Complexes 1‐Ln were typically prepared using Schlenk line techniques rather than more common glove box protocols, by the reduction of the parent Ln(III) complexes [Ln(...
Deuterium labelling of organic compounds is an important process in chemistry. We report the first example of photocatalytic dehalogenative deuteration of both arylhalides and alkylhalides (40 substrates) over a metal‐organic framework, MFM‐300(Cr), using CD3CN as the deuterium source at room temperature. MFM‐300(Cr) catalyses high deuterium incorp...
Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conv...
We examine lanthanide (Ln)-ligand bonding in a family of early Ln3+ complexes [Ln(Cptt)3] (1-Ln, Ln = La, Ce, Nd, Sm; Cptt = C5H3tBu2-1,3) by pulsed electron paramagnetic resonance (EPR) methods, and provide the first characterization of 1-La and 1-Nd by single crystal XRD, multinuclear NMR, IR and UV/Vis/NIR spectroscopy. We measure electron spin...
General-purpose quantum computation and quantum simulation require multi-qubit architectures with precisely defined, robust interqubit interactions, coupled with local addressability. This is an unsolved challenge, primarily due to scalability issues. These issues often derive from poor control over interqubit interactions. Molecular systems are pr...
Glucose is a key intermediate in cellulose photoreforming for H2 production. This work presents a mechanistic investigation of glucose photoreforming over TiO2 and Pt/m-TiO2 catalysts. Analysis of the intermediates formed in the process confirmed the α-scission mechanism of glucose oxidation forming arabinose (Cn-1 sugar) and formic acid in the ini...
We report the modulation of reactivity of nitrogen dioxide (NO2) in a charged metal–organic framework (MOF) material, MFM‐305‐CH3 in which unbound N‐centres are methylated and the cationic charge counter‐balanced by Cl⁻ ions in the pores. Uptake of NO2 into MFM‐305‐CH3 leads to reaction between NO2 and Cl⁻ to give nitrosyl chloride (NOCl) and NO3⁻...
We report the modulation of reactivity of nitrogen dioxide (NO 2 ) in a charged metal–organic framework (MOF) material, MFM‐305‐CH 3 in which unbound N‐centres are methylated and the cationic charge counter‐balanced by Cl ⁻ ions in the pores. Uptake of NO 2 into MFM‐305‐CH 3 leads to reaction between NO 2 and Cl ⁻ to give nitrosyl chloride (NOCl) a...
Electrochemcial reduction of CO2 to multi-carbon (C2+) products is an important but challenging task. Here, we report the control of structural evolution of two porous Cu(ii)-based materials (HKUST-1 and CuMOP, MOP = metal-organic polyhedra) under electrochemical conditions by adsorption of 7,7,8,8-tetracyanoquinodimethane (TNCQ) as an additional e...
A novel strategy of improving cytotoxicity against metastatic melanoma cells using an oxindolimine copper(ii) complex immobilized and dimerized on a modified Polyhedral Oligomeric Silsesquioxane (POSS) matrix was developed, as revealed by electron paramagnetic resonance (EPR) spectroscopy. An assured correlation between continuous-wave (CW) and pul...
In this work, we report the synthesis of a room-temperature-stable electride (RoSE) reagent, namely K⁺(LiHMDS)e⁻ (1) (HMDS: 1,1,1,3,3,3-hexamethyldisilazide), from accessible starting materials (potassium metal and LiHMDS) via mechanochemical ball milling at 20 mmol scale. Despite its amorphous nature, the presence of anionic electrons in 1, key di...
The production of conjugated C4–C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)‐atomically doped mesoporous silica, denoted as AlNb‐MCM‐41, which affords quantitative conversion of 2‐methyltetrahydrofuran (2‐MTHF) to pentadienes with a...
The production of conjugated C4‐C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)‐atomically doped mesoporous silica, denoted as AlNb‐MCM‐41, which affords quantitative conversion of 2‐methyltetrahydrofuran (2‐MTHF) to pentadienes with a...
Increasing levels of air pollution are driving the need for the development of new processes that take "waste-to-chemicals". Herein, we report the capture and conversion under ambient conditions of a major air pollutant, NO2, using a robust metal-organic framework (MOF) material, Zr-bptc (H4bptc = 3,3',5,5'-biphenyltetracarboxylic acid), comprising...
Understanding the structural and chemical changes that reactive metal-organic frameworks (MOFs) undergo is crucial for the development of new efficient catalysts for electrochemical reduction of CO2. Here, we describe three Bi(iii) materials, MFM-220, MFM-221 and MFM-222, which are constructed from the same ligand (biphenyl-3,3',5,5'-tetracarboxyli...
Natural gas, consisting mainly of methane (CH4), has a relatively low energy density at ambient conditions (~36 kJ l−1). Partial oxidation of CH4 to methanol (CH3OH) lifts the energy density to ~17 MJ l−1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely chal...
A new nitronyl‐nitroxide ligand (H2L) featuring alcoholic and phenolic groups has been synthesised starting from 2‐hydroxy‐3‐(hydroxymethyl)‐5‐methylbenzaldehyde (A). Using this ligand, three 2p–4 f binuclear complexes have been obtained and crystallographically characterized: [Ln2(HL)2(hfac)4], (Ln=Gd 1, Tb 2, Dy 3). Apart from the desired compoun...
The presence of active sites in metal-organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a s...
Heterometallic lanthanide [LnLn'] coordination complexes that are accessible thermodynamically are very scarce because the metals of this series have very similar chemical behaviour. Trinuclear systems of this category have not been reported. A coordination chemistry scaffold has been shown to produce molecules of type [LnLn'Ln] of high purity, i.e...
The Front Cover shows that N‐terminal acetylation of α‐synuclein shifts the binding from the N‐terminus to His50 and significantly slows down the binding reaction. More information can be found in the Article by Liming Ying and co‐workers.
Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we functionalized the previously reporte...
The interaction between α‐synuclein (αSyn) and Cu²⁺ has been suggested to be closely linked to brain copper homeostasis. Disruption of copper levels could induce misfolding and aggregation of αSyn, and thus contribute to the progression of Parkinson's disease (PD). Understanding the molecular mechanism of αSyn‐Cu²⁺ interaction is important and cont...
Self-assembly and characterisation of a supramolecular trigonal bipyramidal iron cage containing an [FeIII(μ2-F)6(FeII)3]3+ star motif at its core is reported. The complex can be formed in a one step reaction using an heterotopic ligand that supports site-specific incorporation of iron in three distinct electronic configurations: low-spin FeII, hig...
Manganese(II) xanthate complexes of the form [Mn(S2COR)2(TMEDA)], where TMEDA = tetramethylethylenediamine and R = methyl (1), ethyl (2), n-propyl (3), n-butyl (4), n-pentyl (5), n-hexyl (6), and n-octyl (7), have been synthesized and structures elucidated using single-crystal X-ray diffraction. Complexes 1–7 were used as molecular precursors to sy...
Disproportionation, where a chemical element converts its oxidation state to two different ones, one higher and one lower, underpins the fundamental chemistry of metal ions. The overwhelming majority of uranium disproportionations involve uranium(III) and (V), with a singular example of uranium(IV) to uranium(V/III) disproportionation known, involv...
Metal-organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited method...
Electroactive metal-organic frameworks (MOFs) are an attractive class of materials owing to their multifunctional 3-dimensional structures, the properties of which can be modulated by changing the redox states of the components. In order to realise both fundamental and applied goals for these materials, a deeper understanding of the structure-funct...
In situ growth of the metal-organic framework material MFM-300(Fe) on an ultra-thin sheet of graphitic carbon nitride (g-C3N4) has been achieved via exfoliation of bulk carbon nitride using supercritical CO2. The resultant hybrid structure, CNNS/MFM-300(Fe), comprising carbon nitride nanosheets (CNNS) and MFM-300(Fe), shows excellent performance to...
Mechanically chelating ligands have untapped potential for the engineering of metal ion properties. Here we demonstrate this principle in the context of CoII‐based single‐ion magnets. Using multi‐frequency EPR, susceptibility and magnetization measurements we found that these complexes show some of the highest zero field splittings reported for fiv...
Construction of C-C bonds via reductive coupling of aldehydes and ketones is hindered by the highly negative reduction potential of these carbonyl substrates, particularly ketones, and this renders the formation of ketyl radicals extremely endergonic. Here, we report the efficient activation of carbonyl compounds by the formation of specific host-g...
Selective oxidation of benzylic C−H compounds to ketones is important for the production of a wide range of fine chemicals, and is often achieved using toxic or precious metal catalysts. Herein, we report the efficient oxidation of benzylic C−H groups in a broad range of substrates under mild conditions over a robust metal–organic framework materia...
A fundamental part of characterizing any metal complex is understanding its electronic ground state, for which magnetometry provides key insight. Most uranium(IV) complexes exhibit low-temperature magnetic moments tending to zero, consistent with a non-degenerate spin-orbit ground state. However, there is a growing number of uranium(IV) complexes w...
The oxidation of benzylic C−H groups in a broad range of substrates under mild conditions has been achieved using a robust metal–organic framework, MFM-170, incorporating redox-active [Cu2II(O2CR)4] paddlewheel nodes. EPR spectroscopy and synchrotron X-ray diffraction have identified the critical role of the paddlewheel moiety in activating the oxi...
Mechanically interlocked ligands enable predictable metal ion coordination, offering a new strategy to engineer their properties. A series of field-induced CoII single-ion magnets illustrates this principle. The predictable coordination behaviour of the rotaxane enables remarkably accurate calculation of their zero-field splittings, which are in ag...
Mechanically chelating ligands have untapped potential for the engineering of metal ion properties by providing reliable control of the number, nature and geometry of donor atoms, akin to how a protein cavity controls the properties of bound metal ions. Here we demonstrate this principle in the context of Co<sup>II</sup>-based single-ion magnets. U...
Ammonia (NH3) is a promising energy resource owing to its high hydrogen density. However, its widespread application is restricted by the lack of efficient and corrosion-resistant storage materials. Here, we report high NH3 adsorption in a series of robust metal-organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). MFM-300(M) (M = Fe,...
Here we explore the electronic structure of the diiron complex [(dppf)Fe(CO)3]0/+ [1
0/+
; dppf = 1,1'-bis(diphenylphosphino)ferrocene] in two oxidation states by an advanced multitechnique experimental approach. A combination of magnetic circular dichroism, X-ray absorption and emission, high-frequency electron paramagnetic resonance (EPR), and Mö...
Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within...
Efficient catalytic conversion of NO2 to non-harmful species remains an important target for research. State-of-the-art deNOx processes are based upon ammonia (NH3)-assisted selective catalytic reduction (NH3-SCR) over Cu-exchanged zeolites at elevated temperatures. Here, we describe a highly efficient non-thermal plasma (NTP) deNOx process catalyz...
Quantum coherence is a fundamental property of electron spins that could be exploited in quantum computers for the processing of information. Within quantum calculation protocols, information is encoded in two-level quantum objects (Qubits) and processed by the operations of logical quantum gates (or Qugates). Examples of qubits include electronic...
A series of heterometallic [TiIV7MIII] rings are reported which contain a single paramagnetic metal centre, either FeIII or CrIII. The structures contain an octagon of metals bridged by oxides within the ring and pivalate ligands outside the ring. The structures encapsulate a single cation, either a secondary ammonium cation or a cesium. Multi-freq...
Electrochemical reduction of carbon dioxide is a clean and highly attractive strategy for the production of organic products. However, this is hindered severely by the high negative potential required to activate carbon dioxide. Here, we report the preparation of a copper-electrode onto which the porous metal–organic framework [Cu 2 (L)] [H 4 L = 4...
Four 3d-4f hetero-polymetallic complexes [Fe2Ln2((OCH2)3CR)2(O2C
t
Bu)6(H2O)4] (where Ln = La (1 and 2) and Gd (3 and 4); and R = Me (1 and 3) and Et (2 and 4)) are synthesized and analyzed using elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and SQUID magnetometry. Crystal structures are obtained for both...
Propeller-like lanthanide complexes with suitable chiral ligand scaffolds are highly desired as they combine chirality and magnetic bistability. However, the library of relevant chiral molecules is quite limited. Herein we present the preparation, structures, magnetic behavior as well as EPR studies of a series of propeller-shaped lanthanide Single...
Nitrogen dioxide (NO2) is a toxic air pollutant and efficient abatement technologies are important to mitigate the many associated health and environmental problems. Here we report the reactive adsorption of NO2 in a redox-active metal-organic framework (MOF), MFM-300(V). Adsorption of NO2 induces the oxidation of V(III) to V(IV) centres in MFM-300...
Propeller-like lanthanide complexes with suitable chiral ligand scaffolds are highly desired as they combine chirality and magnetic bistability. However, the library of relevant chiral molecules is quite limited. Herein we present the preparation, structures, magnetic behavior as well as EPR studies of a series of propeller-shaped lanthanide Single...
Organometallic lanthanide (Ln) chemistry is dominated by complexes that contain substituted cyclopentadienyl (CpR) ligands. Closely related phospholyls have received less attention, and although they have proven utility in stabilising low oxidation state Ln complexes the trivalent Ln chemistry of these ligands is limited in comparison. Herein, we s...
A counterintuitive ligand design to induce a spin‐crossover in otherwise high‐spin complexes was devised for 2,6‐bis(pyrazol‐3‐yl)pyridines by choosing bulky substituents, the ortho‐functionalized phenyl groups. The tribute to a Russian avant‐garde artist Kazimir Malevich in the artwork shows it as a traditional ‘tool’ to set the right balance betw...
Gaining a fundamental understanding of charge transfer mechanisms in three-dimensional Metal-Organic Frameworks (MOFs) is crucial to the development of electroactive and conductive porous materials. These materials have potential in applications in porous conductors, electrocatalysts and energy storage devices, however the structure-property relati...
The molecular design of spin‐crossover complexes relies on controlling the spin state of a transition metal ion by proper chemical modifications of the ligands. Herein, the first N,N’‐disubstituted 2,6‐bis(pyrazol‐3‐yl)pyridines (3‐bpp) are reported that, against the common wisdom, induce a spin‐crossover in otherwise high‐spin iron(II) complexes b...
A homoleptic gadolinium(III) complex with the smallest helicene-type ligand 1,10-phenanthroline-N,N’-dioxide (phendo) [Gd(phendo)4](NO3)3·xMeOH (phendo = 1,10-phenanthroline-N,N’-dioxide, MeOH = methanol) shows slow relaxation of magnetization characteristic for Single Ion Magnets (SIM) despite negligible magnetic anisotropy confirmed by ab initio...
Cu-modified zeolites have enormous potential as the catalysts facilitating the conversion of methane to methanol. It becomes important to investigate the active sites and the reaction mechanisms involved. In this paper, several spectroscopic methods such as UV-vis diffuse reflectance spectroscopy (UV-vis DRS), pulse electron paramagnetic resonance...
Despite their importance as mechanistic models for heterogeneous Haber Bosch ammonia synthesis from dinitrogen and dihydrogen, homogeneous molecular terminal metal-nitrides are notoriously unreactive towards dihydrogen, and only a few electron-rich, low-coordinate variants demonstrate any hydrogenolysis chemistry. Here, we report hydrogenolysis of...
The efficient production of light olefins from renewable biomass is a vital and challenging target to achieve future sustainable chemical processes. Here we report a hetero-atomic MFI-type zeolite (NbAlS-1), over which aqueous solutions of γ-valerolactone (GVL), obtained from biomass-derived carbohydrates, can be quantitatively converted into buten...
Air pollution by nitrogen oxides, NOx, is a major problem, and new capture and abatement technologies are urgently required. Here, we report a metal–organic framework (Manchester Framework Material 520 (MFM-520)) that can efficiently confine dimers of NO2, which results in a high adsorption capacity of 4.2 mmol g–1 (298 K, 0.01 bar) with full rever...
Little is known about the chemistry of the 2‐arsaethynolate anion, but to date it has exclusively undergone fragmentation reactions when reduced. Herein, we report the synthesis of [U(TrenTIPS)(OCAs)] (2, TrenTIPS=N(CH2CH2NSiiPr3)3), which is the first isolable actinide‐2‐arsaethynolate linkage. UV‐photolysis of 2 results in decarbonylation, but th...
We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal-organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host fram...
During our attempts to prepare paddlewheel actinide-molybdenum complexes of the type [(X)An(MesNPR2)3Mo(CO)3] (Mes= 2,4,6-trimethylphenyl; X = Cl or I; An = U or Th; R = iPr or Ph) we have found that under certain conditions acetonitrile insertion reactions occur to give the heterobimetallic bridging ketimido species [ClAn(μ-MesNPiPr2)2(μ-MesNPiPr2...
A fundamental bonding model in coordination and organometallic chemistry is the synergic, donor–acceptor interaction between a metal and a neutral π-acceptor ligand in which the ligand σ donates to the metal, which π back-bonds to the ligand. This interaction typically involves a metal with an electron-rich, mid-, low- or even negative oxidation st...
Molecules that are the size of small proteins are difficult to make. The most frequently examined route is via self-assembly, and one particular approach involves molecular nano-capsules, where ligands are designed that will enforce the formation of specific polyhedra of metals within the core of the structure. Here we show that this approach can b...
There is a need for biofunctionalised magnetic nanoparticles for many biomedical applications, including MRI contrast agents that have a range of surface properties and functional groups. A library of eleven adducts, each formed by condensing a reducing sugar with a catechol hydrazide, for nanoparticle functionalisation has been created using a hig...
The proposal that paramagnetic transition metal complexes could be used as qubits for quantum information processing (QIP) requires that the molecules retain the spin information for a sufficient length of time to allow computation and error correction. Therefore, understanding how the electron spin-lattice relaxation time (T1) and phase memory tim...
We report a six coordination Dy III single-molecule magnet (SMM) with an energy barrier of 1110 K for thermal relaxation of magnetization. The pure compound shows no retention of magnetization even...
The chemistry of 2‐phosphaethynolate is burgeoning, but there remains much to learn about this ligand, for example its reduction chemistry is scarce as this promotes P‐C‐O fragmentations or couplings. Here, we report that reduction of [U(TrenTIPS)(OCP)] (TrenTIPS=N(CH2CH2NSiPrⁱ3)3) with KC8/2,2,2‐cryptand gives [{U(TrenTIPS)}2{μ‐η²(OP):η²(CP)‐OCP}]...
A simplified uniaxial anisotropic Heisenberg model is proposed which describes the observed magnetic properties of a family of the Cr 7 M (M = Cd, Ni, Mn) molecular rings, and allows the determination of the coupling parameters which are all transferable among this family of molecular nanomagnets.
The chemistry of 2‐phosphaethynolate is burgeoning, but there remains much to learn about this ligand, for example its reduction chemistry is scarce as this promotes P‐C‐O fragmentations or couplings. Here, we report that reduction of [U(TrenTIPS)(OCP)] (TrenTIPS = N(CH2CH2NSiPri3)3) with KC8/2,2,2‐cryptand gives [{U(TrenTIPS)}2{μ‐η2(OP):η2(CP)‐OCP...
Molecular uranium-nitrides are now well known, but there are no isolable molecular thorium-nitrides outside of cryogenic matrix isolation experiments. We report that treatment of [M(TrenDMBS)(I)] (M = U, 1; Th, 2; TrenDMBS = {N(CH2CH2NSiMe2Bu
t
)3}3-) with NaN3 or KN3, respectively, affords very rare examples of actinide molecular square and trian...
Here we show that a structure containing a polymeric interlockingdaisy chain is obtained from the reaction of an inorganic–organic[2]rotaxane [HB{CrIII7NiII(l-F)8(O2CtBu)16}], whereBis an organicthread terminated with a bi-pyridyl unit, with an oxo-centered metalcarboxylate triangle [FeIII2CoII(l3-O)(O2CtBu)6(HO2CtBu)3].
Ricinoleic acid, extracted from the castor bean, is a cheap, abundant and naturally sourced capping agent for nanocrystals that offers the ability to functionalise the as‐synthesized nanocrystals through the use of the hydroxyl group, an advantage over oleic acid obtained from olives. In this work, we demonstrate the use of zinc and manganese ricin...
We report the preparation of four heterobimetallic uranium- and thorium-molybdenum paddlewheel complexes. The characterisation data calculations suggest the presence of Mo→An σ-interactions in all cases. These complexes represent unprecedented actinide-group...
We report a six coordinate DyIII single-molecule magnet
(SMM) with an energy barrier of 1110 K for thermal relaxation of
magnetization. The sample shows no retention of magnetization
even at 2 K and this led us to find a good correlation between the
blocking temperature and the Raman relaxation regime for SMMs.
The key parameter is the relaxation t...
Using electron spins within molecules for quantum information processing (QIP) was first proposed by Leuenberger and Loss (1), who showed how the Grover algorithm could be mapped onto a Mn12 cage (2). Since then several groups have examined two-level (S = ½) molecular spin systems as possible qubits (3-12). There has also been a report of the imple...
Nitrogen dioxide (NO2) is a major air pollutant causing significant environmental1,2 and health problems3,4. We report reversible adsorption of NO2 in a robust metal-organic framework. Under ambient conditions, MFM-300(Al) exhibits a reversible NO2 isotherm uptake of 14.1 mmol g-1, and, more importantly, exceptional selective removal of low-concent...
[2] and [3] hybrid rotaxanes are reported based on {Ti7M} rings (M is a trivalent metal such as FeIII or GaIII). NMR studies show that [2]rotaxanes can act as molecular shuttles, while EPR studies of [3]rotaxanes show weak interactions between the paramagnetic components of the supramolecular assemblies. [2]‐ und [3]Hybridrotaxane auf der Grundlage...
[2] and [3] hybrid rotaxanes are reported based on {Ti7M} rings (M is a trivalent metal such as FeIII or GaIII). NMR studies show that [2]rotaxanes can act as molecular shuttles, while EPR studies of [3]rotaxanes show weak interactions between the paramagnetic components of the supramolecular assemblies. Ti7M's all in a spin: All[2] and [3] hybrid...
Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligan...