
Alexander J. BlakeUniversity of Nottingham | Notts · School of Chemistry
Alexander J. Blake
PhD
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1,257
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Introduction
We are engaged in a systematic search to discover new
phenomena, primarily by means of applying high pressures of up to 150,000 atmospheres to single crystals of transition metal coordination complexes. The phenomena we have observed so far include changes in geometry at metal centres, polymerisation, conformational rearrangements and colour changes which can be unexpected, extreme or multiple.
Additional affiliations
September 1976 - August 1979
Education
September 1972 - June 1976
Publications
Publications (1,257)
Over recent decades, the rapid development of lanthanide-based coordination polymers (Ln-based CPs) has been made possible by the implementation of crystal engineering concepts in the design of materials with desired properties. Because of the effects of lanthanide ions on properties of Ln-based CPs, it is essential to understand the ability of the...
The reaction between a two-coordinate Co(II) diaryl complex and “GaI” affords 2,6-Pmp2C6H3CoGa3I5, in a new geometry for a heavier group 13-transition metal cluster. Experimental and computational investigations show that this...
Herein we report the synthesis of three heteroleptic first‐row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)‐carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt‐catalysed hy...
A two-coordinate Fe(II) m-terphenyl complex acts as a precatalyst for the hydroamination of isocyanates, affording urea and biuret derivatives, with product selectivity accomplished via modification of the reaction conditions. Using a more nucleophilic amine facilitates the insertion of up to four isocyanates into the N–H bond, affording triuret an...
Co-crystals of thiocyanuric acid (TCA) and five multi-topic bases are reported and their structures compared. The adducts of all five co-crystals form two-dimensional hydrogen bonded sheets which are either stacked or interpenetrated. Strong N-H···N hydrogen bonds between TCA and the N-heterocyclic bases are supplemented by pairs of longer, weaker...
A Special Issue on the topic of Electron Crystallography, now available in the August 2019 issue of Acta Crystallographica, Section B, contains contributions which we hope will interest readers of IUCrJ.
The reactions of 1,1'-bis(3-methyl-4-imidazolin-2-selone)methane (L1) and 1,2-bis(3-methyl-4-imidazolin-2-selone)ethane (L2) with mesityltellurenyl iodide (MesTeI) [Mes = 2,4,6-Me3C6H2] yielded the neutral [L1·2MesTeI].2CH2Cl2 and the ionic [L2·MesTe]2(MesTeI2)2 compounds, respectively, which were characterized by X-ray diffraction analysis. DFT (m...
Sulfenyl, selenenyl, and tellurenyl cations [RE]+ (E = S, Se, Te), displaying singly bonded chalcogen atoms E with four non-bonding electrons, are extremely reactive species due to their diradical character resulting from a triplet ground state.1
Examples of authentic tellurenyl cations stabilized as 1:2 CT adducts with neutral donors are extremel...
A magnesium complex (1) featuring a bidentate aminopyridinato ligand is a remarkably selective catalyst for the dehydrocoupling of amine‐boranes. This reaction proceeds to completion with low catalyst loadings (1 mol %) under mild conditions (60 °C), exceeding previously reported s‐block systems in terms of selectivity, rate, and turnover number (T...
We describe here the synthesis and coordination properties of three new derivatives of [9]aneN3 containing phenyl/quinoline pendant arm derivatives (L1, L2 and L3, respectively) also featuring urea (L1-L2) or amide (L3) functions as “non-innocent” spacers. At first L1, L2 and L3 were studied considering the interaction with a series of anions (AcO-...
In this paper, we describe experimental evidence of a change in the emission energy as a function of the Au-Au distance. We have employed a luminescent complex exhibiting an aurophilic interaction, which is weak enough to allow its length to be modified by external pressure but rigid enough to confer structural stability on the complex. By determin...
Two coordination complexes, [Mn2(pydco)2(phen)2(H2O)2]·2H2O (1) and [Mn(3-pyco)2(H2O)4] (2), based on Mn(II), pyridine-2,5-dicarboxylic acid N–oxide (H2pydco) and 1,10-phenanthroline (phen) as organic ligands have been synthesized and characterized by elemental analyses, infrared spectroscopy and single crystal X-ray diffraction. We have synthesize...
In order to develop new porous materials for applications in gas separations such as natural gas upgrading, landfill gas processing and acetylene purification it is vital to gain understanding of host-substrate interactions at a molecular level. Herein we report a series of six isoreticular metal-organic frameworks (MOFs) for selective gas adsorpti...
We report an unprecedented ligand-based binding domain for D2 within a porous metal-organic framework (MOF) material as confirmed by neutron powder diffraction studies of D2-loaded MFM-132a. A tight pocket of 6 Å diameter is formed by the close packing of three anthracene panels, and it is here rather than the open metal sites where D2 binds prefer...
Carbon monoxide is a key C1 feedstock for the industrial production of hydrocarbons, where it is used to make millions of tonnes of chemicals, fuels, and solvents per annum. Many transition metal complexes can coordinate CO, but the formation of new C-C bonds in well-defined compounds from the scission and subsequent coupling of two or more CO moie...
A new anionic coordination complex of Zn(II) containing the highly pre-organized ligand 1,10-phenanthroline-2,9-dicarboxylate (PDA), (H3O)2[Zn(PDA)2]·2CH3NO2·2H2O·(1), has been synthesized by solvothermal methods and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The last of these techniques reveale...
Two new Cu(II) complexes [Cu(L1)(N3)](1) and [Cu(L1)(NCS)]n(2), where HL1 ((E)-4-((2(dimethylamino)ethylimino)methyl)-5-(hydroxymethyl)-2-methylpyridin-3-ol) is a N,N,O-donor Schiff base ligand, have been synthesized. These complexes were characterized on the basis of spectroscopic, electrochemical, and other physicochemical properties. X-ray cryst...
The reactivity of the 2-arylselanyl pyridine derivatives L1-L4 towards dihalogens X2 (X = I, Br) and interhalogens IX (X = Cl, Br) was studied in CHCl3 or CH3CN. The solid products obtained were structurally characterized and their nature points out the preference for CT spoke adducts and for seesaw insertion adducts to be formed at the N-donor and...
Three binuclear [NiFe] complexes, incorporating {Fe(CO)2(CN)2} units, reproduce the key features of the active sites of the [NiFe] hydrogenases. [Ni(N2S3)Fe(CO)2(CN)2] undergoes reversible Ni-centered oxidation to form a formal NiIIIFeII species that possesses an electronic structure that is analogous to that proposed for the Ni−C state of the [NiF...
Controlled assembly of two-dimensional (2D) supramolecular organic frameworks (SOFs) has been demonstrated through a binary strategy in which 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)naphthalene (2), generated in situ by oxidative dehydrogenation of 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)naphthalene (1), is coupled in a 1:1 ratio...
This corrects the article DOI: 10.1038/ncomms14137.
High pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB4- [H4TCHB = 3,3',5,5'-tetrakis(4-carboxyphenyl)-2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl] and {M6(µ-OH)8(OH)8(COO)8} clusters, confirm negative linear compressibility (NLC) behavior along...
The structural characterization of single crystals of di-4-pyridyl-substituted 3,4,9,10-perylenetetracarboxylic diimide reveals a surprising triple helical arrangement. The intermolecular interactions that lead to such an arrangement are investigated by Hirshfeld surface analysis and indicate that the supramolecular structure arises due to a combin...
Group 1 salts containing carbazolido NNN pincer ligands are pre-catalysts for the dehydrogenation of Me2NH·BH3. NMR monitoring and DOSY studies show a heavy dependence on the metal and solvent employed,...
Two- and three-coordinate manganese m-terphenyl complexes are precatalysts for the dehydrogenation of dimethylamine-borane (Me2NH·BH3) affording one equivalent of molecular hydrogen and [Me2N–BH2]2. Experimental studies into the nature of the catalyst indicate that small changes in the coordination environment give rise to significant differences i...
This paper describes a total synthesis of the terpene-derived natural product aritasone via the hetero-Diels-Alder [4+2] cyclodimerisation of pinocarvove, which represents the proposed biosyntheic route. The hetero-Diels-Alder dimerisation of pinocarvone did not proceed under standard conditions, and ultra-high pressure (19.9 kbar) was required. As...
Herein, we report the synthesis and the anion binding properties of a family of N,N′-diphenylureas L1-L15, bearing on the aromatic ring(s) halogens (chlorine and iodine) and/or nitro or trifluoromethyl electron-withdrawing groups. The analysis of the crystal structures obtained from single crystal X-ray diffraction experiments shows that self-assem...
Natural gas (methane, CH4) is widely considered as a promising energy carrier for mobile applications. Maximising the storage capacity is the primary goal for the design of future storage media. Here we report the CH4 storage properties in a family of isostructural (3,24)-connected porous materials, MFM-112a, MFM-115a and MFM-132a with different li...
A historical challenge: Gas-phase electron diffraction and single-crystal X-ray diffraction are both established techniques, but they were both pushed to their limits by the challenge posed by the highly flexible tetranitromethane molecule. New approaches had to be developed for the structure of the molecule to be elucidated.
Eine historische Herausforderung: Gasphasen-Elektronenbeugung und Einkristall-Röntgenbeugung sind etablierte Techniken, stießen aber bei dem hoch flexiblen Molekül Tetranitromethan bisher an ihre Grenzen. Neue Ansätze mussten entwickelt werden, bevor nun die Struktur dieses Moleküls aufgeklärt werden konnte.
Bromination of (AsPh2)2S leads to cleavage of the sulfide bridge to give AsPh2Br when 1mol of bromine is used but with 2mols the product is the polybromide, [AsPh2Br2]2[Br8], containing the previously unknown [AsPh2Br2]⁺ cation and a rare [(Br3)⁻...(Br2)...(Br3)⁻] ensemble whose short (yet not covalent) Br2...Br3 contacts have previously supported...
Square-planar diamagnetic nickel(II) complexes 5a and 5b containing 16-membered diamino-diimino ligands were prepared from the corresponding open-chain complexes 2a and 2b via condensation with o-phthalic dialdehyde in methanol. The solid-state structure of the starting complex 2b revealed the cisoid conformation of aryl groups compared to the tran...
The reactions between magnesium or zinc alkyls and 1,8-bis(triorganosilyl)diaminonaphthalenes afford the 1,8-bis(triorganosilyl)diamidonaphthalene complexes with elimination of alkanes. The reaction between 1,8-C10H6(NSiMePh2H)2 and one or two equivalents of Mg(n)Bu2 affords two complexes with differing coordination environments for the magnesium;...
Significance
A family of stable porous materials incorporating organic linkers and Cu(II) cations is reported. Their pores can be altered systematically by elongation of the ligands allowing a strategy of selective pore extension along one dimension. These materials show remarkable gas adsorption properties with high working capacities for CH 4 (0....
The phosphinimine, trimethylsilyl-substituted BIPM ligand [BIPM = bis(iminophosphorano)methanide] has been used to stabilise CH(Ph2PNSiMe3)2MgFe(η⁵-C5H5)(CO)2 (1), which is a structurally authenticated complex exhibiting a direct, unsupported bond between an alkaline earth metal and a transition metal. The FTIR-measured carbonyl stretching frequenc...
The first transition metal catalyzed hydrophosphination of isocyanates is presented. The use of low-coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion of isocyanates into the P−H bond of diphenylphosphine to yield phosphinodicarboxamides [Ph2PC(=O)N(R)C(=O)N(H)R], a new family of derivatized organophosphorus compo...
The first transition metal catalyzed hydrophosphination of isocyanates is presented. The use of low-coordinate iron(II) precatalysts leads to an unprecedented catalytic double insertion of isocyanates into the P−H bond of diphenylphosphine to yield phosphinodicarboxamides [Ph2PC(=O)N(R)C(=O)N(H)R], a new family of derivatized organophosphorus compo...
Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, beca...
Crystallographic Information File for 1TB
Crystallographic Information File for 2Ce
Crystallographic Information File for 2Tb
Supplementary Figures, Supplementary Tables, Supplementary Methods and Supplementary References
Crystallographic Information File for 3Th
Crystallographic Information File for 2Pr
Crystallographic Information File for 3Ce
Crystallographic Information File for 5Th
Crystallographic Information File for 5U
Crystallographic Information File for 3U
Crystallographic Information File for 6Pr
Crystallographic Information File for 6Tb
A family of Cu(II)-based metal–organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H 2 L ¹ (4′-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H 2 L ² (4′′-(pyridin-4-yl)-1,1′:4′,1′′-terphenyl-3,5-dicarboxylic acid) and H 2 L ³ (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each c...
The tetranuclear heterometallic complex [Li2Zn2(piv)6(py)2] (1, where piv(-) = pivalate and py = pyridine) has been successfully employed as a presynthesized node for the construction of four porous metal-organic frameworks (MOFs) [Li2Zn2(R-bdc)3(bpy)]·solv (2-R, R-bdc(2-); R = H, Br, NH2, NO2) by reaction with 4,4'-bipyridine (bpy) and terephthala...
Two- and three-coordinate m-terphenyl complexes of manganese and iron are efficient catalysts for the selective cyclotrimerisation of primary aliphatic isocyanates affording isocyanurates in short reaction times and under mild conditions.
Nine dioxidomolybdenum(VI) complexes were synthesized by the reaction of MoO3 with tridentate hydrazone Schiff base ligands obtained from the reaction of aromatic acid hydrazides (3-hydroxy-2-naphthoic acid hydrazide, 4-pyridine carboxylic acid hydrazide or 2-furane carboxylic acid hydrazide) and ortho-hydroxy aldehyde derivatives (5-iodo-2-hy...
Chromeazurol B (Na2HL) is a pH-sensitive (halochromic) dye based on a hydroxytriarylmethane core and two carboxylate functional groups, which makes it suitable for the synthesis of coordination polymers. Two new coordination polymers [NaZn4(H2O)3(L)3]·3THF·3H2O (1) and [Zn3(H2O)3(μ2- OH2)(μ3-OH)(HL)2(H2L)]·2THF·3H2O (2) incorporating Chromeazurol B...
An amide-functionalised metal organic frame-work (MOF) material, MFM-136, shows a high CO2 uptake of 12.6 mmol g-1 at 20 bar and 298 K. MFM-136 is the first example of acylamide pyrimidyl isophthalate MOF without open metal sites, and thus provides a unique platform to study guest bind-ing, particularly the role of free amides. Neutron diffraction...
An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO2 uptake of 12.6 mmol g⁻¹ at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffractio...
Two cyclotriveratrylene-based ligands H3L1 and H3L2 have been synthesised using microwave heating and used in the formation of 1 [Zn2(L1)(DMA)2(CH3COO)] and 2 [Zn6(L2)4(DMA)6(H2O)5] (DMA = N,N-dimethylacetamide). 1 displays an unusual trigonal paddlewheel node geometry, while Zn(II) paddlewheels are observed in 2. However the stacking of CTV molecu...
A binuclear Cu(II) complex of formula [Cu(L¹Hpy)Cl]2(ClO4)2 (1), where L¹H2 is a new tridentate ligand, formed by condensation of 2-aminomethyl pyridine and pyridoxal (one of the forms of vitamin B6), has been synthesized. X-ray crystal structure determination shows that in this complex two Cu(II) ions are interconnected by complementary hydroxymet...
Molecules of tris(2,2′-bipyridine-4-thiomethyl-BEDT-TTF)iron(II) (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) assemble in pairs to form a novel supramolecular capsular structure in the solid state. Three BEDT-TTF residues from one complex lie in the three grooves between coordinated bipyridines of the other complex, and vice versa, to form a...
Selective adsorption of SO2 is realized in a porous metal-organic framework material, and in-depth structural and spectroscopic investigations using X-rays, infrared, and neutrons define the underlying interactions that cause SO2 to bind more strongly than CO2 and N2 .
In two binuclear complexes of formula [Cu2(AnthenMe2)2(μ1,3-SCN)2(NCS)2] (1) and [Cu2(AnthenMe2)2(μ1,1-N3)2(N3)2] (2), where AnthenMe2 is the bidentate N,N-donor Schiff base formed by anthracene-9-aldehyde and N,N-dimethylethylenediamine, each Cu(II) centre adopts a square pyramidal geometry with N4S and N5 coordination environments for 1 and 2, re...
The Co(III) and Ni(II) complexes [Co(L2)2(bpy)]Cl (1) and [Ni(L2)2(phen)] (2) (where L2 is a monoanionic bidentate hydrazone ligand and bpy = 2,2’-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by infra-red, UV-Vis, ESI-MS spectroscopies and elemental analyses. Complexes 1 and 2 were structurally characterized by si...
The three reported phases of the mononuclear macrocyclic PdII complex [PdCl2([9]aneS2O)] [(1); [9]aneS2O = 1-oxa-4,7-dithiacyclononane] were each studied up to pressures exceeding 9 GPa using high-pressure single-crystal X-ray diffraction. The α- and γ-phases both exhibit smooth compression of the unit-cell parameters with third-order Birch–Murnagh...
A family of four tris-carboxylic acid ligands 1,3,5-tris(4’-carboxybiphenyl-2-yl)benzene (H3L1), 1,3,5-tris-2-carboxyphenylbenzene (H3L2), 1,3,5-tris(4’’carboxy-para-terphenyl-2-yl)benzene (H3L3) and 1,3,5-tris(3’-carboxybiphenyl-2-yl)benzene (H3L4) have been synthesised and reacted with first row transition metal cations to give nine complexes whi...
High pressure crystallographic studies on [1,4-C6H4{PPh2(AuCl)}2] (1) reveal the largest pressure-induced contraction of an aurophilic interaction observed for any Au(I) complex; Hirshfeld surface analysis and Raman spectroscopy reveals the presence of several types of intermolecular interaction, which play an important role in the behaviour of 1 a...
Two metal-organic framework materials, MFM-130 and MFM-131 (MFM = Manchester Framework Material), have been synthesized using two oligoparaxylene (OPX) tetracarboxylate linkers containing four and five aromatic rings, respectively. Both fof-type non-interpenetrated networks contain Kagomé lattice layers comprising [Cu2(COO)4] paddlewheel units and...
We report comparable levels of covalency in cerium- and uranium-carbon multiple bonds in the iso-structural carbene complexes [M(BIPMTMS)(ODipp)2] [M = Ce (1), U (2), Th (3); BIPMTMS = C(PPh2NSiMe3)2; Dipp = C6H3-2,6-Pri2] whereas for M = Th the M=C bond interaction is much more ionic. On the basis of single crystal X-ray diffraction, NMR, IR, EPR,...
Metal-organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga2(OH)2(L)] (H4L = biphenyl-3,3',5,5'-tetracarboxylic acid), designated as MFM-300(Ga2...
Additional experimental details and figures
Additional experimental details and figures
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and...