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Metal-organic nanotubes (MONTs) are 1-dimensional crystalline porous materials that are formed from ligands and metals in a manner identical to more typical 3-dimensional metal-organic frameworks (MOFs). MONTs form anisotropically in one dimension making them excellent candidates for linker engineering for control of chemical composition and spacing. A novel series of MONTs was synthesized utilizing a mixture of 1,2,4-ditriazole ligands containing both a fully protonated aryl moiety and its tetrafluorinated analog in ratios of, 0 : 1, 1 : 4, 1 : 1, 4 : 1, and 1 : 0, respectively. All MONTs were characterized by both bulk and nanoscale measurements, including SCXRD, PXRD, ssNMR and TEM, to determine the resulting co-polymer architecture (alternating, block, or statistical) and the ligand ratios in the solid materials. All characterization methods point towards statistical copolymerization of the materials in a manner analogous to 3D MOFs, all of which notably could be achieved without destructive analytical methods., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

To further the development of boron heterocyclic compounds that are useful to medicinal chemistry, we demonstrate how the class of compounds known as the diazaborines can be elaborated to produce an exceptionally close structural mimic of a natural estrogen. After building progressively closer models, a benzyloxy-substituted formylphenylboronic acid was ultimately condensed with a hydroxymethylated β-hydrazinocyclopentenone to give, after debenzylation, an isosteric mimic (diazaborine 1) of the naturally-occurring estrogen equilenin and the prototype of a new class of boron heterocycle estrogen mimics. X-ray crystallography revealed the prototype to be planar, with a transmolecular interoxygen distance virtually identical to that found in equilenin and with a strong hydrogen-bond-donating hydroxyl group. From this it can be anticipated that members of this unique class of boron heterocycle estrogen mimics will be found to possess useful biological properties. Furthermore, the prototype was found to fluoresce in the deep blue region of the visible spectrum, and so the development of members serving as light-emitting probes in biochemical and biological studies can also be anticipated., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

An atomic view of a main aqueous conformation of cyclosporine A (CycA), an important 11-amino-acid macrocyclic immunosuppressant, is reported. For decades, it has been a grand challenge to determine the conformation of free CycA in an aqueous-like solution given its poor water solubility. Using a combination of X-ray and single-crystal neutron diffraction, we unambiguously resolve a unique conformer (A1) with a novel cis -amide between residues 11 and 1 and two water ligands that stabilize hydrogen bond networks. NMR spectroscopy and titration experiments indicate that the novel conformer is as abundant as the closed conformer in 90/10 (v/v) methanol/water and is the main conformer at 10/90 methanol/water. Five other conformers were also detected in 90/10 methanol/water, one in slow exchange with A1, another one in slow exchange with the closed form and three minor ones, one of which contains two cis amides Abu2-Sar3 and MeBmt1-MeVal11. These conformers help better understand the wide spectrum of membrane permeability observed for CycA analogues and, to some extent, the binding of CycA to protein targets.

An isostructural set of macrocyclic tetra-N-heterocyclic carbene (NHC) complexes were synthesized on late lanthanides including Lu, Yb, Ho, Dy, and Gd. They were characterized by single-crystal X-ray diffraction, multinuclear NMR, electrochemistry, and SQUID magnetometry. Solid-state structures show that all complexes are in a highly distorted square-pyramidal geometry with an axial HMDS ligand. 1 H NMR for Lu, Yb, and Dy demonstrates that these geometries are maintained in solution. Electrochemical measurements on the Yb complex show that the NHCs are very strong σ-donors compared to other organometallic Yb complexes. Magnetic measurements of the Yb and Dy complexes reveal slow relaxation of the magnetization in both complexes. The highly anisotropic Dy complex possesses an energy barrier to spin reversal of 52.42 K/36.43 cm -1 and waist-restricted hysteresis up to 2.8 K. Finally, an 18-atom macrocycle variant of the Lu complex was synthesized for comparison in reactivity and stability. These complexes are the first lanthanides prepared with macrocyclic NHCs and suggest that NHCs may be a promising ligand for developing single-molecule magnets.

Highly-symmetrical, thorium and uranium octakis-carbene 'sandwich' complexes have been prepared by 'sandwiching' the An(iv) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms. The complexes were characterized by a range of experimental methods and DFT calculations. X-ray crystallography confirms the geometry at the metal centre can be set by the size of the macrocyclic ring, leading to either square prismatic or square anti-prismatic shapes; the geometry of the latter is retained in solution, which also undergoes reversible, electrochemical one-electron oxidation or reduction for the uranium variant. DFT calculations reveal a frontier orbital picture that is similar to thorocene and uranocene, in which the NHC ligands show almost exclusively σ-donation to the metal without π-backbonding., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The unconventional clathrates, Cs 8 Zn 18 Sb 28 and Cs 8 Cd 18 Sb 28 , were synthesized and reinvestigated. These clathrates exhibit unique and extensive superstructural ordering of the clathrate-I structure that was not initially reported. Cs 8 Cd 18 Sb 28 orders in the Ia 3̄ d space group (no. 230) with 8 times larger volume of the unit cell in which most framework atoms segregate into distinct Cd and Sb sites. The structure of Cs 8 Zn 18 Sb 28 is much more complicated, with an 18-fold increase of unit cell volume accompanied by significant reduction of symmetry down to P 2 (no. 3) monoclinic space group. This structure was revealed by a combination of synchrotron X-ray diffraction and electron microscopy techniques. A full solid solution, Cs 8 Zn 18- x Cd x Sb 28 , was also synthesized and characterized. These compounds follow Vegard's law in regard to their primitive unit cell sizes and melting points. Variable temperature in situ synchrotron powder X-ray diffraction was used to study the formation and melting of Cs 8 Zn 18 Sb 28 . Due to the heavy elements comprising clathrate framework and the complex structural ordering, the synthesized clathrates exhibit ultralow thermal conductivities, all under 0.8 W m -1 K -1 at room temperature. Cs 8 Zn 9 Cd 9 Sb 28 and Cs 8 Zn 4.5 Cd 13.5 Sb 28 both have total thermal conductivities of 0.49 W m -1 K -1 at room temperature, among the lowest reported for any clathrate. Cs 8 Zn 18 Sb 28 has typical p-type semiconducting charge transport properties, while the remaining clathrates show unusual n-p transitions or sharp increases of thermopower at low temperatures. Estimations of the bandgaps as activation energy for resistivity dependences show an anomalous widening and then shrinking of the bandgap with increasing Cd-content., Competing Interests: Authors declare no conflict of interests., (This journal is © The Royal Society of Chemistry.)