Synthesis and coordination chemistry of 2-(di-2-pyridylamino)pyrimidine; structural aspects of spin crossover in an Fe(II) complex

This paper was accepted on February 26 20122-(Di-2-pyridylamino)pyrimidine (L), a potentially ditopic tetradentate ligand, was synthesized from commercially available di-2-pyridylamine and 2-chloropyrimidine. Despite being capable of bridging two metal atoms with bidentate chelation of both metal centres, L prefers to chelate or bridge through the more basic pyridyl donors of the di-2-pyridylamine moiety. Mononuclear trans-[Fe(NCS)2(L)2] and [Cu(L)2(H2O)](BF4)2•H2O complexes, and a discrete [Ag2(L)4](PF6)2 metallomacrocycle were isolated and structurally characterized by X-ray crystallography. A mononuclear palladium complex [PdCl2(L)]•(solvate), where solvate = ½H2O or CH2Cl2, was also readily obtained in 71% yield. One example of the ligand acting as a bis(bidentate) bridging ligand was observed in a dinuclear [(PdCl2)2(L)]•¾H2O complex that was obtained only in very low yield (ca. 3%) from the reaction that produced [PdCl2(L)]•½H2O. trans-[Fe(NCS)2(L)2] undergoes a temperature dependent HS-LS (HS = high spin; LS = low spin) crossover at ca. 205 K that was 2 observed by X-ray crystallography and magnetic measurements and attempts were made to understand the structural basis of this process. Despite efforts to isolate examples of L bridging two iron(II) centres, only the mononuclear trans-[Fe(NCS)2(L)2] species could be obtained.Rachel S. Crees, Boujemma Moubaraki, Keith S. Murray, and Christopher J. Sumb

Synthesis and X-ray crystal structure of a bridging trispiran ligand

The document attached has been archived with permission from the publisher.Spiro[3,3]heptane-2,6-dispiro-4,5-diazafluorene (4) has been synthesized in three steps from 1,10-phenanthroline. It crystallizes in the orthorhombic space group P212121 and has the two 4,5-diazafluorene metal binding domains mutually orthogonal.Peter J. Steel and Christopher J. Sumb

Using hinged ligands to target structurally flexible copper(II) MOFs

First published online 23 Aug 2013Here we report two new flexible MOFs based on a bis-pyrazolylmethane 'hinged' link design that favours the formation of two distinct structural nodes within the resulting 2-D and 3-D structures. The less sterically demanding ligand H₂bcppm affords a 2-D layered MOF, {Cu₂[Cuˡˡ(NO₃)₂(bcppm)₂](DMF)₂}•2DMF (1), constructed from copper(II) paddlewheel and mononuclear octahedral copper(II) nodes. The use of a more sterically encumbered tetramethyl analogue H₂bcpdmpm induces a dramatic twisting of the ligand backbone that yields a 3-D MOF{Cu₄[Cuˡ(bcpdmpm)₂]₂(EtOH)₂(H₂O)₂}(NO₃)₂•12DMF (2) formed from a very similar mix of nodes, specifically copper(II) paddlewheel clusters and mononuclear tetrahedrally coordinated copper(I) centres. Herein we describe the crystal structures, solid-state flexibility, and gas adsorption properties of both materials.Witold M. Bloch, Christian J. Doonan and Christopher J. Sumb

Towards microstructured optical fibre sensors: surface analysis of silanised lead silicate glass

While protocols to surface functionalise silica glass platforms are well-established, the surface coating of other glass types have received limited attention. Here we fully characterise the surface attachment of a fluoroionophore on extruded lead silicate glass slides and demonstrate these slides as a model for investigating the surface chemistry in a microstructured optical fibre (MOF). This model system allows the utilization of multiple, complementary surface-sensitive techniques that cannot be used within the internal surface of the fibre structure. In characterising the fluoroionophore attachment, we observe that the fluorescence intensity from fluorescence imaging, the atomic nitrogen percentage measured by X-ray photoelectron spectroscopy (XPS), the carbonyl bond component (287.5 eV) in the XPS high resolution carbon spectrum, and Principal Component Analysis (PCA) of the time-of-flight secondary ion mass spectrometry (ToF-SIMS) data can be used to provide relative quantification of the concentration of an attached fluoroionophore. We also show the first use of ToF-SIMS imaging and depth profiling of the Pb content within a glass substrate to provide information on the coverage provided by the coating and the relative thickness of an organic coating. Combined, these techniques provide a comprehensive picture of the coated glass surface that facilitates fibre sensor development.Herbert T. C. Foo, Heike Ebendorff-Heidepriem, Christopher J. Sumby, Tanya M. Monr

Chemokine-cleaving Streptococcus pyogenes protease SpyCEP is necessary and sufficient for bacterial dissemination within soft tissues and the respiratory tract.

Published versio

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs, and other topologies

The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with CuI and/or CuII cations that show a remarkable range of framework topologies and structures. Complex [CuI4CuII1.5(L1)3(CN)6]·CN·n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu3(L2)4(H2O)3]·6(OTf)·n(DMSO) 2 and [Cu2(L3)2Br2(H2O)(DMSO)]·2Br·n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (43.123)(42.122) topology or a coordination chain. Complex [Cu2(L1)2(OTf)2(NMP)2(H2O)2]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.62.8)(62.8)(4.62.82) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF4·2(CH3CN)·H2O 5 features a 2D network of 63 topology while the CuII analogue [Cu2(L1)2(NMP)(H2O)]·4BF4·12NMP·1.5H2O 6 has an interpenetrating (10,3)-b type structure and complex [Cu2(L2)2Br3(DMSO)]·Br·n(DMSO) 7 has a 2D network of 4.82 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C60 through soaking the crystals in a toluene solution

Does functionalisation enhance CO2 uptake in interpenetrated MOFs? An examination of the IRMOF-9 series

The effect of pore functionalisation (-I, -OH, -OCH3) on a series of topologically equivalent, interpenetrated metal-organic frameworks (MOFs) was assessed by both simulation and experiment. Counter-intuitively, a decreased affinity for CO2 was observed in the functionalised materials, compared to the non-functionalised material. This result highlights the importance of considering the combined effects of network topology and chemical functionality in the design of MOFs for enhanced CO2 adsorptionRavichandar Babarao, Campbell J. Coghlan, Damien Rankine, Witold M. Bloch, Gemma K. Gransbury, Hiroshi Sato, Susumu Kitagawa, Christopher J. Sumby, Matthew R. Hill and Christian J. Doona

The role of visual spatial attention in audiovisual speech perception

International audienc