2D to 3D Reconstruction of Boron-Linked Covalent-Organic Frameworks.

The transformation of two-dimensional (2D) covalent-organic frameworks (COFs) into three-dimensions (3D) is synthetically challenging, and it is typically addressed through interlayer cross-linking of alkene or alkyne bonds. Here, we report the first example of the chemical reconstruction of a 2D COF to a 3D COF with a complete lattice rearrangement facilitated by base-triggered boron hybridization. This chemical reconstruction involves the conversion of trigonal boronate ester linkages to tetrahedral anionic spiroborate linkages. This transformation reticulates the coplanar, closely stacked square cobalt(II) phthalocyanine (PcCo) units into a 3D perpendicular arrangement. As a result, the pore size of COFs expands from 2.45 nm for the initial 2D square lattice (sql) to 3.02 nm in the 3D noninterpenetrated network (nbo). Mechanistic studies reveal a base-catalyzed boronate ester protodeboronation pathway for the formation of the spiroborate structure.

Fingerprints of Chalcogen Bonding Revealed Through 77Se-NMR.

77Se-NMR is used to characterise several chalcogen bonded complexes of derivatives of the organoselenium drug ebselen, exploring a range of electron demand. NMR titration experiments support the intuitive understanding that chalcogen bond donors bearing more electron withdrawing substituents give rise stronger chalcogen bonds. The chemical shift of the selenium nucleus is also shown to move upfield as it participates in a chalcogen bond. Solid-state NMR is used to explore chalcogen bonding in co-crystals. Due to the lack of molecular reorientation on the NMR timescale in the solid state, the shape of the chemical shift tensor can be determined using this technique. A range of co-crystals are shown to have extremely large chemical shift anisotropy, which suggests a strongly anisotropic electron density distribution around the selenium atom. A single crystal NMR experiment was conducted using one of the co-crystals, affording the absolute orientation of the chemical shift tensor within the crystal. This showed that the selenium nucleus is strongly shielded in the direction of the chalcogen bond (due to the approach of the lone pair of the Lewis base), and strongly deshielded in the perpendicular direction. The orientation of the deshielded axis is consistent with the presence of a second σ-hole which is not participating in a chalcogen bond, showing the profound effect of electron density anisotropy on the chemical shift.

Risk classification of low-lying coral reef islands and their exposure to climate threats.

The bio-physical responses of low-lying coral islands to climate change are of concern. These islands exist across a broad range of bio-physical conditions, and vulnerabilities to rising and warming seas, ocean acidification and increased storminess. We propose a risk-based classification that scores 6 island eco-morphometric attributes and 6 bio-physical ocean/climate conditions from recent open-access data, to assign islands with respect to 5 risk classes (Very Low, Low, Moderate, High and Very High). The potential responses of 56 coral islands in Australia's jurisdiction (Coral Sea, NW Shelf and NE Indian Ocean) to climate change is considered with respect to their bio-physical attributes and eco-morphometrics. None of the islands were classed as Very Low risk, while 8 were classed as Low (14.3 %), 34 were Moderate (60.7 %), 11 were High (19.6 %), and 3 were Very High (5.4 %). Islands in the Very High risk class (located on the NW Shelf) are most vulnerable due to their small size (mean 10 Ha), low elevation (mean 2.6 m MSL), angular/elongated shape, unvegetated state, below average pH (mean 8.05), above average rates of sea-level rise (SLR; mean 4.6 mm/yr), isolation from other islands, and frequent tropical storms and marine heatwaves. In contrast, islands in the Low (and Very Low) risk class are less vulnerable due to their large size (mean 127 Ha), high elevation (mean 8.5 m MSL), sub-angular/round shape, vegetated state, near average pH (mean 8.06), near average SLR rates (mean 3.9 mm/yr), proximity to adjacent islands, and infrequent cyclones and marine heatwaves. Our method provides a risk matrix to assess coral island vulnerability to current climate change related risks and supports future research on the impacts of projected climate change scenarios. Findings have implications for communities living on coral islands, associated ecosystem services and coastal States that base their legal maritime zones on these islands.

Soft Hydrogen-Bonded Organic Frameworks Constructed Using a Flexible Organic Cage Hinge.

Soft porous crystals combine flexibility and porosity, allowing them to respond structurally to external physical and chemical environments. However, striking the right balance between flexibility and sufficient rigidity for porosity is challenging, particularly for molecular crystals formed by using weak intermolecular interactions. Here, we report a flexible oxygen-bridged prismatic organic cage molecule, Cage-6-COOH, which has three pillars that exhibit "hinge-like" rotational motion in the solid state. Cage-6-COOH can form a range of hydrogen-bonded organic frameworks (HOFs) where the "hinge" can accommodate a remarkable 67° dihedral angle range between neighboring units. This stems both from flexibility in the noncovalent hydrogen-bonding motifs in the HOFs and the molecular flexibility in the oxygen-linked cage hinge itself. The range of structures for Cage-6-COOH includes two topologically complex interpenetrated HOFs, CageHOF-2α and CageHOF-2ß. CageHOF-2α is nonporous, while CageHOF-2ß has permanent porosity and a surface area of 458 m2 g-1. The flexibility of Cage-6-COOH allows this molecule to rapidly transform from a low-crystallinity solid into the two crystalline interpenetrated HOFs, CageHOF-2α and CageHOF-2ß, under mild conditions simply by using acetonitrile or ethanol vapor, respectively. This self-healing behavior was selective, with the CageHOF-2ß structure exhibiting structural memory behavior.

Experimental Confirmation of a Predicted Porous Hydrogen-Bonded Organic Framework.

Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm-3 and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g-1 , as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date.

High-resolution structural study on pyridin-3-yl ebselen and its N-methylated tosylate and iodide derivatives.

The crystal structure of the pyridine-substituted benzisoselenazolinone 2-(pyridin-3-yl)-2,3-dihydro-1,2-benzoselenazol-3-one (C12H8N2OSe, 2), related to the antioxidant ebselen [systematic name: 2-phenyl-1,2-benzoselenazol-3(2H)-one, 1], is characterized by strong intermolecular N...Se(-N) chalcogen bonding, where the N...Se distance of 2.3831 (6) Šis well within the sum of the van der Waals radii for N and Se (3.34 Å). This strong interaction results in significant lengthening of the internal N-Se distance, consistent with significant population of the Se-N σ* antibonding orbital. Much weaker intermolecular O...Se chalcogen bonding occurs between the amide-like O atom in 2 and the less polarized C-Se bond in this structure. Charge density analysis of 2 using multipole refinement of high-resolution data allowed the electrostatic surface potential for 2 to be mapped, and clearly reveals the σ-hole at the extension of the Se-N bond as an area of positive electrostatic potential. Topological analysis of the electron-density distribution in 2 was carried out within the Quantum Theory of Atoms in Molecules (QTAIM) framework and revealed bond paths and (3,-1) bond critical points (BCPs) for the N...Se-N moiety consistent with a closed-shell interaction; however, the potential energy term is suggestive of electron sharing. Analysis of the electron localization function (ELF) for the strong N...Se and the weak O...Se chalcogen-bonding interactions in the structure of 2 suggest significant electron sharing in the former interaction, and a largely electrostatic interaction in the latter. Conversion of 2 to its N-methylated derivatives by reaction with methyl iodide [1-methyl-3-(3-oxo-2,3-dihydro-1,2-benzoselenazol-2-yl)pyridin-1-ium iodide, C13H11N2OSe+·I-] and methyl tosylate [1-methyl-3-(3-oxo-2,3-dihydro-1,2-benzoselenazol-2-yl)pyridin-1-ium toluenesulfonate trihydrate, C13H11N2OSe+·C7H7O3S-·3H2O] removes the possibility of N...Se chalcogen bonding and instead structures are obtained where the iodide and tosylate counter-ions fulfill the role of chalcogen-bond acceptors, with a strong I-...Se interaction in the iodide salt and a weaker p-Tol-SO3-...Se interaction in the tosylate salt.

Packing-induced selectivity switching in molecular nanoparticle photocatalysts for hydrogen and hydrogen peroxide production.

Molecular packing controls optoelectronic properties in organic molecular nanomaterials. Here we report a donor-acceptor organic molecule (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9H-carbazol-3-yl)pyridine-3,5-dicarbonitrile) that exhibits two aggregate states in aqueous dispersions: amorphous nanospheres and ordered nanofibres with π-π molecular stacking. The nanofibres promote sacrificial photocatalytic H2 production (31.85 mmol g-1 h-1) while the nanospheres produce hydrogen peroxide (H2O2) (3.20 mmol g-1 h-1 in the presence of O2). This is the first example of an organic photocatalyst that can be directed to produce these two different solar fuels simply by changing the molecular packing. These different packings affect energy band levels, the extent of excited state delocalization, the excited state dynamics, charge transfer to O2 and the light absorption profile. We use a combination of structural and photophysical measurements to understand how this influences photocatalytic selectivity. This illustrates the potential to achieve multiple photocatalytic functionalities with a single organic molecule by engineering nanomorphology and solid-state packing.

Creating communities and communicating science during COVID-19: From Coast2Coast to Coast2Cast.

The global COVID-19 pandemic has seen extended lockdowns, isolation periods and travel restrictions across many countries around the world since early 2020. Some countries, such as Australia and New Zealand, closed their international borders in early 2020 preventing researchers travelling to other parts of the world. To facilitate the exposure of our students' work, and for them to meet international researchers, as well as foster a sense of coastal community, we started a zoominar series (seminars via Zoom) in April 2020. The Coast2Coast zoominar series had therefore humble origins but we soon discovered that there was an appetite for more widely sharing science across the coastal research disciplines. The Coast2Coast zoominar grew rapidly, attracting researchers from many countries around the world who presented and attended fortnightly online seminars. In just one year and a half we had 38 presentations with roughly 1900 attendees, creating a sense of community and belonging for the researchers involved. In early 2021, two of the co-authors, Giovanni (GC) and Ana (AVC) decided to expand and take this sense of community further creating the Coast2Cast podcast series, where researchers are asked research and non-research questions. In only 7 months, the podcasts have attracted more than 3700 listeners. Importantly, while the main prerequisite was high-quality and impactful research, diversity and inclusion were also a priority in selecting and inviting speakers for the zoominars and guests for the podcast. Importantly, our survey results suggest that there is a place for online events similar to Coast2Coast and Coast2Cast in a pandemic-free future, and that the coastal community involved has greatly benefited from such initiatives.

Synthesis of acyloin natural products by Mukaiyama hydration.

The acyloin natural products are a family of bioactive compounds isolated from fungi and myxobacteria. The total synthesis of 7 members of the acyloin family was achieved via a HWE reaction followed by Mukaiyama-Isayama hydration, using novel Co(II) and Co(III) Schiff base SALPN complexes as catalysts for the key enone hydration step. Furthermore, we have shown that a mild acyloin rearrangement is possible under Mukaiyama hydration conditions, which was crucial in the success of this approach.

Simulating chalcogen bonding using molecular mechanics: a pseudoatom approach to model ebselen.

The organoselenium compound ebselen has recently been investigated as a treatment for COVID-19; however, efforts to model ebselen in silico have been hampered by the lack of an efficient and accurate method to assess its binding to biological macromolecules. We present here a Generalized Amber Force Field modification which incorporates classical parameters for the selenium atom in ebselen, as well as a positively charged pseudoatom to simulate the σ-hole, a quantum mechanical phenomenon that dominates the chemistry of ebselen. Our approach is justified using an energy decomposition analysis of a number of density functional theory-optimized structures, which shows that the σ-hole interaction is primarily electrostatic in origin. Finally, our model is verified by conducting molecular dynamics simulations on a number of simple complexes, as well as the clinically relevant enzyme SOD1 (superoxide dismutase), which is known to bind to ebselen. Graphical Abstract Ebselen is an organoselenium drug that has shown promise for the treatment of a number of conditions. Computational modelling of drug-target complexes is commonly performed to determine the likely mechanism of action, however this is difficult in the case of ebselen, as an important mode of interaction is not simulated using current techniques. We present here an extension to common methods, which accurately captures this interaction.

CHAL336 Benchmark Set: How Well Do Quantum-Chemical Methods Describe Chalcogen-Bonding Interactions?

We present the CHAL336 benchmark set-the most comprehensive database for the assessment of chalcogen-bonding (CB) interactions. After careful selection of suitable systems and identification of three high-level reference methods, the set comprises 336 dimers each consisting of up to 49 atoms and covers both σ- and π-hole interactions across four categories: chalcogen-chalcogen, chalcogen-π, chalcogen-halogen, and chalcogen-nitrogen interactions. In a subsequent study of DFT methods, we re-emphasize the need for using proper London dispersion corrections when treating noncovalent interactions. We also point out that the deterioration of results and systematic overestimation of interaction energies for some dispersion-corrected DFT methods does not hint at problems with the chosen dispersion correction but is a consequence of large density-driven errors. We conclude this work by performing the most detailed DFT benchmark study for CB interactions to date. We assess 109 variations of dispersion-corrected and dispersion-uncorrected DFT methods and carry out a detailed analysis of 80 of them. Double-hybrid functionals are the most reliable approaches for CB interactions, and they should be used whenever computationally feasible. The best three double hybrids are SOS0-PBE0-2-D3(BJ), revDSD-PBEP86-D3(BJ), and B2NCPLYP-D3(BJ). The best hybrids in this study are ωB97M-V, PW6B95-D3(0), and PW6B95-D3(BJ). We do not recommend using the popular B3LYP functional nor the MP2 approach, which have both been frequently used to describe CB interactions in the past. We hope to inspire a change in computational protocols surrounding CB interactions that leads away from the commonly used, popular methods to the more robust and accurate ones recommended herein. We would also like to encourage method developers to use our set for the investigation and reduction of density-driven errors in new density functional approximations.

Optimising molecular rotors to AIE fluorophores for mitochondria uptake and retention.

Molecular rotors exhibit fluorescence enhancement in a confined environment and thus have been used extensively in biological imaging. However, many molecular rotors suffer from small Stokes shift and self-aggregation caused quenching. In this work, we have synthesised a series of red emissive molecular rotors based on cationic α-cyanostilbene. Profoundly enhanced aggregation-induced emission (AIE) properties and greatly widened Stokes shifts can be achieved by molecular engineering. With specificity to stain mitochondria, we demonstrate a simple approach to achieve cell uptake and retention upon tuning the pyridinium substituent of the dyes.

Geologically controlled sandy beaches: Their geomorphology, morphodynamics and classification.

Beaches that are geologically controlled by rock and coral formations are the rule, not the exception. This paper reviews the current understanding of geologically controlled beaches, bringing together a range of terminologies (including embayed beaches, shore platform beaches, relict beaches, and perched beaches, among others) and processes, with the aim of exploring the multiple ways in which geology influences beach morphology and morphodynamics. We show how in addition to sediment supply, the basement geology influences where beaches will form by providing accommodation, and in the cross-shore, aspects of rock platform morphology such as elevation and slope are also important. Geologically controlled beaches can have significant variations in sediment coverage with seasons and storms, and geological controls have fundamental influences on their contemporary morphodynamics. This includes wave shadowing by headlands and rock/coral formations inducing strong alongshore gradients in wave energy, resulting in corresponding variations in morphodynamic beach state and storm response. Geologically-induced rip currents including shadow rips, deflection rips and mega-rips that can develop on embayed beaches during storms, are an integral feature of the nearshore circulation and morphodynamics of geologically controlled beaches. We bring these processes together by presenting a conceptual model of alongshore and cross-shore levels of geological control. In the longshore dimension, this ranges from beaches that are slightly embayed, through to highly embayed beaches where headlands dominate the entire beach morphodynamic response. In the cross-shore dimension, this ranges from beaches without discernible geological controls, through to relict beaches above the influence of the contemporary littoral zone. Given the prevalence of geologically controlled beaches along the world's coasts, it is paramount for coastal management to consider how these beaches differ from unconstrained beaches and avoid applying inappropriate models and tools, especially with our uncertain future climate.

Experimental evidence of chalcogen bonding at oxygen.

An o-nitro-O-aryl oxime was observed to exhibit a short OO contact, which exhibited characteristics consistent with a chalcogen bond. The O-N bond length of the oxime was appreciably longer than the expected value, and NBO calculations indicated the presence of a n(O) → σ(O-N) orbital delocalisation. Topological analysis of the experimental electron density of two analogues shows the presence of a bond path between the two oxygen atoms, with ρ(r) and ∇2ρ(r) values consistent with an electrostatic interaction. Finally, electrostatic potential calculations indicate the presence of a σ-hole, the "smoking gun" indicating a Ch-bond. These results are unusual as oxygen is not typically considered to be a Ch-bond donor, especially in unactivated systems such as oximes.

Structures of the hydrate and dihydrate forms of the DNA-binding radioprotector methyl-pro-amine.

Methyl pro-amine {N,N,3-trimethyl-4-[6-(4-methyl-piperazin-1-yl)-1H,3'H-[2,5'-bibenzo[d]imidazol]-2'-yl]aniline}, C28H35N7O2, crystallized as both a dihydrate, C28H31N7·2H2O, and monohydrate, C28H31N7·H2O, form from water in the presence of ß-cyclo-dextrin, in the P21/c and P21/n space groups, respectively. The two structures adopt different conformations and tautomeric forms as a result of the differing crystal packing as dictated by hydrogen-bonding inter-actions. The dihydrate crystallizes as a three-dimensional hydrogen-bonded network, while the monohydrate crystallizes as a two-dimensional hydrogen-bonded network.