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Post-synthetic modification (PSM) of the interpenetrated diamondoid metal-organic framework (Me 2 NH 2 )[In(BDC-NH 2 ) 2 ] (BDC-NH 2 = aminobenzenedicarboxylate) SHF-61 proceeds quantitatively in a single-crystal-to-single-crystal manner to yield the acetamide derivative (Me 2 NH 2 )[In(BDC-NHC(O)Me) 2 ] SHF-62 . Continuous breathing behaviour during activation/desolvation is retained upon PSM, but pore closing now leads to ring-flipping to avert steric clash of amide methyl groups of the modified ligands. This triggers a reduction in the amplitude of the breathing deformation in the two dimensions associated with pore diameter, but a large increase in the third dimension associated with pore length. The MOF is thereby converted from predominantly 2D breathing (in SHF-61 ) to a distinctly 3D breathing motion (in SHF-62 ) indicating a decoupling of the pore-width and pore-length breathing motions. These breathing motions have been mapped by a series of single-crystal diffraction studies.

The metal–organic framework (Me2NH2)2[Cd(NO2BDC)2] (SHF-81) comprises flattened tetrahedral Cd(O2CR)42− nodes, in which Cd(II) centres are linked via NO2BDC2− ligands (2-nitrobenzene-1,4-dicarboxylate) to give a doubly interpenetrated anionic network, with charge balanced by two Me2NH2+ cations per Cd centre resident in the pores. The study establishes that this is a twinned α-quartz-type structure (trigonal, space group P3x21, x = 1 or 2), although very close to the higher symmetry β-quartz arrangement (hexagonal, P6x22, x = 2 or 4) in its as-synthesised solvated form [Cd(NO2BDC)2]·2DMF·0.5H2O (SHF-81-DMF). The activated MOF exhibits very little N2 uptake at 77 K, but shows significant CO2 uptake at 273–298 K with an isosteric enthalpy of adsorption (ΔHads) at zero coverage of −27.4 kJ mol−1 determined for the MOF directly activated from SHF-81-DMF. A series of in situ diffraction experiments, both single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD), reveal that the MOF is flexible and exhibits breathing behaviour with observed changes as large as 12% in the a- and b-axes (|Δa|, |Δb| < 1.8 Å) and 5.5% in the c-axis (|Δc| < 0.7 Å). Both the solvated SHF-81-DMF and activated/desolvated SHF-81 forms of the MOF exhibit linear negative thermal expansion (NTE), in which pores that run parallel to the c-axis expand in diameter (a- and b-axis) while contracting in length (c-axis) upon increasing temperature. Adsorption of CO2 gas at 298 K also results in linear negative expansion (Δa, Δb > 0; Δc < 0; ΔV > 0). The largest change in dimensions is observed during activation/desolvation from SHF-81-DMF to SHF-81 (Δa, Δb < 0; Δc > 0; ΔV < 0). Collectively the nine in situ diffraction experiments conducted suggest the breathing behaviour is continuous, although individual desolvation and adsorption experiments do not rule out the possibility of a gating or step at intermediate geometries that is coupled with continuous dynamic behaviour towards the extremities of the breathing amplitude.

Metal–organic framework nanosheets (MONs) are attracting increasing attention as a diverse class of two-dimensional materials derived from metal–organic frameworks (MOFs). The principles behind the design of layered MOFs that can readily be exfoliated to form nanosheets, however, remain poorly understood. Here we systematically investigate an isoreticular series of layered MOFs functionalized with alkoxy substituents in order to understand the effect of substituent alkyl chain length on the structure and properties of the resulting nanosheets. A series of 2,5-alkoxybenzene-1,4-dicarboxylate ligands (O2CC6H2(OR)2CO2, R = methyl–pentyl, 1–5, respectively) was used to synthesize copper paddle-wheel MOFs. Rietveld and Pawley fitting of powder diffraction patterns for compounds Cu(3–5)(DMF) showed they adopt an isoreticular series with two-dimensional connectivity in which the interlayer distance increases from 8.68 Å (R = propyl) to 10.03 Å (R = pentyl). Adsorption of CO2 by the MOFs was found to increase from 27.2 to 40.2 cm3 g–1 with increasing chain length, which we attribute to the increasing accessible volume associated with increasing unit-cell volume. Ultrasound was used to exfoliate the layered MOFs to form MONs, with shorter alkyl chains resulting in higher concentrations of exfoliated material in suspension. The average height of MONs was investigated by AFM and found to decrease from 35 ± 26 to 20 ± 12 nm with increasing chain length, with the thinnest MONs observed being only 5 nm, corresponding to five framework layers. These results indicate that careful choice of ligand functionalities can be used to tune nanosheet structure and properties, enabling optimization for a variety of applications.

From October through mid-December 2015, influenza activity remained low in most regions of the United States. Activity began to increase in late December 2015 and continued to increase slowly through early February 2016. Influenza A viruses have been most frequently identified, with influenza A (H3N2) viruses predominating during October until early December, and influenza A (H1N1)pdm09 viruses predominating from mid-December until early February. Most of the influenza viruses characterized during that time are antigenically similar to vaccine virus strains recommended for inclusion in the 2015-16 Northern Hemisphere vaccines. This report summarizes U.S. influenza activity* during October 4, 2015-February 6, 2016, and updates the previous summary (1).

The syntheses of three series of complexes designed with self-complementary motifs for formation of halogen bonds between an iodotetrafluorophenyl ligand and a halide ligand at square-planar nickel are reported, allowing structural comparisons of halogen bonding between all four halides C 6 F 4 I⋯X-Ni (X = F, Cl, Br, I). In the series trans-[NiX(2,3,5,6-C 6 F 4 I)(PEt 3 ) 2 ] 1pX and trans-[NiX(2,3,4,5-C 6 F 4 I)(PEt 3 ) 2 ] (X = F, Cl, Br, I) 1oX, the iodine substituent on the benzene ring was positioned para and ortho to the metal, respectively. The phosphine substituents were va ried in the series, trans-[NiX(2,3,5,6-C 6 F 4 I)(PEt 2 Ph) 2 ] (X = F, I) 2pX. Crystal structures were obtained for the complete series 1pX, and for 1oF, 1oCl, 1oI and 2pI. All these complexes exhibited halogen bonds in the solid state, of which 1pF exhibited unique characteristics with a linear chain, the shortest halogen bond d(C 6 F 4 I⋯F-Ni) = 2.655(5) Å and the greatest reduction in halogen bond distance (I⋯F) compared to the sum of the Bondi van der Waals radii, 23%. The remaining complexes form zig-zag chains of halogen bonds with distances also reduced with respect to the sum of the van der Waals radii. The magnitude of the reductions follow the pattern F > Cl ∼ Br > I, 1pX > 1oX, consistent with the halogen bond strength following the same order. The variation in the I⋯X-Ni angles is consistent with the anisotropic charge distribution of the halide ligand. The temperature dependence of the X-ray structure of 1pF revealed a reduction in halogen bond distance of 0.055(7) Å on cooling from 240 to 111 K. Comparison of three polymorphs of 1oI shows that the halogen bond geometry may be altered significantly by the crystalline environment. The effect of the halogen bond on the 19 F NMR chemical shift in the solid state is demonstrated by comparison of the magic-angle spinning NMR spectra of 1pF and 1oF with that of a complex incapable of halogen bond formation, trans-[NiF(C 6 F 5 )(PEt 3 ) 2 ] 3F. Halogen bonding causes deshielding of δ iso in the component of the tensor perpendicular to the nickel coordination plane. The results demonstrate the potential of fluoride ligands for formation of halogen bonds in supramolecular structures.

During the 2014-15 influenza season in the United States, influenza activity increased through late November and December before peaking in late December. Influenza A (H3N2) viruses predominated, and the prevalence of influenza B viruses increased late in the season. This influenza season, similar to previous influenza A (H3N2)-predominant seasons, was moderately severe with overall high levels of outpatient illness and influenza-associated hospitalization, especially for adults aged ≥65 years. The majority of circulating influenza A (H3N2) viruses were different from the influenza A (H3N2) component of the 2014-15 Northern Hemisphere seasonal vaccines, and the predominance of these drifted viruses resulted in reduced vaccine effectiveness. This report summarizes influenza activity in the United States during the 2014-15 influenza season (September 28, 2014-May 23, 2015) and reports the recommendations for the components of the 2015-16 Northern Hemisphere influenza vaccine.

The role of the closing lecture in a Faraday Discussion is to summarise the contributions made to the Discussion over the course of the meeting and in so doing capture the main themes that have arisen. This article is based upon my Closing Remarks Lecture at the 203(rd) Faraday Discussion meeting on Halogen Bonding in Supramolecular and Solid State Chemistry, held in Ottawa, Canada, on 10-12(th) July, 2017. The Discussion included papers on fundamentals and applications of halogen bonding in the solid state and solution phase. Analogous interactions involving main group elements outside group 17 were also examined. In the closing lecture and in this article these contributions have been grouped into the four themes: (a) fundamentals, (b) beyond the halogen bond, (c) characterisation, and (d) applications. The lecture and paper also include a short reflection on past work that has a bearing on the Discussion.

Control of intermolecular interactions is integral to harnessing self-assembly in nature. Here we demonstrate that control of the competition between hydrogen bonds and halogen bonds, the two most highly studied directional intermolecular interactions, can be exerted by choice of solvent (polarity) to direct the self-assembly of co-crystals. Competitive co-crystal formation has been investigated for three pairs of hydrogen bond and halogen bond donors, which can compete for a common acceptor group. These competitions have been examined in seven different solvents. Product formation has been determined and phase purity has been examined by analysis of powder X-ray diffraction patterns. Formation of hydrogen-bonded co-crystals is favoured from less polar solvents and halogen-bonded co-crystals from more polar solvents. The solvent polarity at which the crystal formation switches from hydrogen-bond to halogen-bond dominance depends on the relative strengths of the interactions, but is not a function of the solution-phase interactions alone. The results clearly establish that an appreciation of solvent effects is critical to obtain control of the intermolecular interactions.

The {Cr8 } metallacrown [CrF(O2 C(t) Bu)2 ]8 , containing a F-lined internal cavity, shows high selectivity for CO2 over N2 . DFT calculations and absorption studies support the multiple binding of F-groups to the C-center of CO2 (C⋅⋅⋅F 3.190(9)-3.389(9) Å), as confirmed by single-crystal X-ray diffraction.

Understanding the behaviour of flexible metal–organic frameworks (MOFs)—porous crystalline materials that undergo a structural change upon exposure to an external stimulus—underpins their design as responsive materials for specific applications, such as gas separation, molecular sensing, catalysis and drug delivery. Reversible transformations of a MOF between open- and closed-pore forms—a behaviour known as ‘breathing’—typically occur through well-defined crystallographic transitions. By contrast, continuous breathing is rare, and detailed characterization has remained very limited. Here we report a continuous-breathing mechanism that was studied by single-crystal diffraction in a MOF with a diamondoid network, (Me2NH2)[In(ABDC)2] (ABDC, 2-aminobenzene-1,4-dicarboxylate). Desolvation of the MOF in two different solvents leads to two polymorphic activated forms with very different pore openings, markedly different gas-adsorption capacities and different CO2 versus CH4 selectivities. Partial desolvation introduces a gating pressure associated with CO2 adsorption, which shows that the framework can also undergo a combination of stepped and continuous breathing.

CDC collects, compiles, and analyzes data on influenza activity year-round in the United States (http://www.cdc.gov/flu/weekly/fluactivitysurv.htm). The influenza season generally begins in the fall and continues through the winter and spring months; however, the timing and severity of circulating influenza viruses can vary by geographic location and season. Influenza activity in the United States increased starting mid-October through December. This report summarizes U.S. influenza activity during September 28-December 6, 2014.

©2016 the Partner Organisations. Solvothermal reaction of Zn(NO3)2·6H2O with di-pyridin-2-yl-[4-(2-pyridin-4-yl-vinyl)-phenyl]-amine (ppvppa) and 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) in H2O and MeCN at 150 °C yielded a two-dimensional (2D) coordination Zn(ii) polymer [Zn(ppvppa)(1,4-NDC)]n (1). Compound 1 was characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and thermogravimetric analysis. Compound 1 consists of dimeric [Zn2(ppvppa)2] units linked by 1,4-NDC bridges to generate a 2D honeycomb network. Either compound 1 or ppvppa alone can detect Hg2+ or MeHgI selectively and with good sensitivity. Upon addition of Hg2+ ions to a MeCN solution of ppvppa, marked changes in the UV-vis and fluorescence spectra are observed, associated with colour changes, which are easily identified by the naked eye. The pyridinyl rings of ppvppa are coordinated to the Hg2+ ion. This motif in the presence of NO3- ions forms a binuclear complex [Hg2(ppvppa)2(NO3)4] (2), which has been characterized as the solvate [Hg2(ppvppa)2(NO3)4]·H2O·4MeCN (2·H2O·4MeCN) by single-crystal X-ray diffraction studies. In aqueous solution, compound 1 emits pale orange light at ambient temperature and the addition of Hg2+ or MeHgI induces an change of fluorescence color from pale orange to blue. Compound 1 is a promising candidate as a sensitive naked-eye indicator for Hg2+ or MeHgI in water under a UV lamp. Introduction to the international collaboration Prof. Lang and Prof. Brammer met with each other in Nanjing, China when Prof. Brammer taught lectures at Nanjing Tech University last November. Prof. Lang's research involves metal sulfide cluster chemistry, design and development of new coordination complex-based catalysts, bioinorganic chemistry related to mimicking metal sites of enzymes and proteins, and so on. Prof. Brammer's research interest covers supramolecular chemistry and crystal engineering, in particular host-guest chemistry and catalysis in metal-organic frameworks, reactions in molecular solids and fundamentals of intermolecular interactions. Both professors recognised their many mutual research interests and decided to initiate an international collaborative project in the area of coordination polymers. Both will visit the partner's lab in China and UK in the near future and expand this project to a higher level.

The coordination polymers [Ag4 (O2 CCF3 )4 (phen)3 ]⋅phen⋅arene (1⋅phen⋅arene) (phen=phenazine; arene=toluene, p-xylene or benzene) have been synthesised from the solution phase in a series of arene solvents and crystallographically characterised. By contrast, analogous syntheses from o-xylene and m-xylene as the solvent yield the solvent-free coordination polymer [Ag4 (O2 CCF3 )4 (phen)2 ] (2). Toluene, p-xylene and benzene have been successfully used in mixed-arene syntheses to template the formation of coordination polymers 1⋅phen⋅arene, which incorporate o- or m-xylene. The selectivity of 1⋅phen⋅arene for the arene guests was determined, through pairwise competition experiments, to be p-xylene>toluene≈benzene>o-xylene>m-xylene. The largest selectivity coefficient was determined as 14.2 for p-xylene:m-xylene and the smallest was 1.0 for toluene:benzene.

During May 24–September 5, 2015, the United States experienced typical low levels of seasonal influenza activity. Influenza A (H1N1)pdm09 (pH1N1), influenza A (H3N2), and influenza B viruses were detected worldwide and were identified sporadically in the United States. All of the influenza viruses collected from U.S. states and other countries during that time have been characterized antigenically and/or genetically as being similar to the influenza vaccine viruses recommended for inclusion in the 2015–16 Northern Hemisphere vaccine. During May 24–September 5, 2015, three influenza variant† virus infections were reported; one influenza A (H3N2) variant virus (H3N2v) from Minnesota in July, one influenza A (H1N1) variant (H1N1v) from Iowa in August, and one H3N2v from Michigan in August.

The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability β (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.1, 1b 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, 5a 4.7, 6a 4.7, 4b 6.9, 5b 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to 1a in carbon tetrachloride (−23.5 ± 0.3 kJ mol–1) interlocks our study with Laurence’s scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of pπ–dπ bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)2], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.

Despite an absence of conventional porosity, the 1D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 ] (1; TMP=tetramethylpyrazine) can absorb small alcohols from the vapour phase, which insert into AgO bonds to yield coordination polymers [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)3 (ROH)2 ] (1-ROH; R=Me, Et, iPr). The reactions are reversible single-crystal-to-single-crystal transformations. Vapour-solid equilibria have been examined by gas-phase IR spectroscopy (K=5.68(9)×10(-5) (MeOH), 9.5(3)×10(-6) (EtOH), 6.14(5)×10(-5) (iPrOH) at 295 K, 1 bar). Thermal analyses (TGA, DSC) have enabled quantitative comparison of two-step reactions 1-ROH→1→2, in which 2 is the 2D coordination polymer [Ag4 (O2 C(CF2 )2 CF3 )4 (TMP)2 ] formed by loss of TMP ligands exclusively from singly-bridging sites. Four polymorphic forms of 1 (1-A(LT) , 1-A(HT) , 1-B(LT) and 1-B(HT) ; HT=high temperature, LT=low temperature) have been identified crystallographically. In situ powder X-ray diffraction (PXRD) studies of the 1-ROH→1→2 transformations indicate the role of the HT polymorphs in these reactions. The structural relationship between polymorphs, involving changes in conformation of perfluoroalkyl chains and a change in orientation of entire polymers (A versus B forms), suggests a mechanism for the observed reactions and a pathway for guest transport within the fluorous layers. Consistent with this pathway, optical microscopy and AFM studies on single crystals of 1-MeOH/1-A(HT) show that cracks parallel to the layers of interdigitated perfluoroalkyl chains develop during the MeOH release/uptake process.

The effect of solvent on the stabilities of complexes involving a single H-bond or halogen-bond (X-bond) has been quantified. Association constants for binary complexes of 4-(phenylazo)phenol, molecular iodine, tetramethylurea and tetramethylthiourea have been measured in fifteen different solvents by UV/vis absorption and 1H NMR titration experiments. The stabilities of the H-bonded complexes decrease by more than three orders of magnitude with increasing solvent polarity. In contrast, the X-bonded complex of molecular iodine with tetramethylthiourea is remarkably insensitive to the nature of the solvent (association constants measured in alkanes and alcohols are similar). The results suggest that, in contrast to H-bonds, where electrostatics determine thermodynamic stability, charge-transfer interactions make a major contribution to the stability of these X-bonded complexes rendering them resistant to increases in solvent polarity.

The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η5-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η5-cyclopentadienyl) is demonstrated by 1H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = −10.9 ± 0.4 and −11.8 ± 0.3 kJ/mol; ΔS° = −38 ± 2 and −34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH° = −7.3 ± 0.1 kJ/mol, ΔS° = −24 ± 1 J/(mol·K)). For the more reactive complexes 2–5, measurements are limited to determination of their low-temperature (212 K) association constants with C6F5I as 2.9 ± 0.2, 2.5 ± 0.1

The essays gathered in this volume explore the difficulties of classifying and conceptualizing the extreme and the excessive. Uniting a broad selection of new research (initially presented as part of the University of Salford’s annual College of Arts and Social Sciences Conference 2011), the collection queries some of the premises surrounding these topics: ideas that are most often presented as a counterpoint to a perceived ‘normality’.\ud Both terrorism/responses to terrorist threat and the grotesque within horror cinema are represented whilst perhaps reflecting that which is deemed outside of the general parameters of acceptability and decency. Yet there is also a focus on subjects that may, at first, be seen as less radical. From alternative representations of authorship to new technology’s attempts at ‘realness’, prose as hysteria through to melodramatic depictions of war and, finally, approaches that aim to challenge the more commonplace critical strategies employed in the assessment of both fine art and fine artists, this collection will be of particular interest to students and scholars prepared to look beyond a concept that may hint at the merely shocking and engage with a more widely interpreted and nuanced critique of extremity and excess.