2,8-Dithia-5-aza-2,6-pyridinophane (L1) has been used as a receptor unit in the construction of the conjugated redox chemosensor 5-ferrocenylmethyl-2,8-dithia-5-aza-2,6-pyridinophane (L3). In order to further explore the coordination chemistry of L1, and comparatively, that of its structural analogue 2,11-dithia-5,8-diaza-2,6-pyridinophane (L2), featuring two secondary nitrogen atoms in the macrocyclic unit, the crystal structures of the new synthesised complexes [Pb(L1)(ClO4)2]·½CH3CN, [Cu(L2)](ClO4)2·CH3CN and [Cd(L2)(NO3)]NO3 were determined by X-ray diffraction analysis. The electrochemical response of L3 towards the metal ions Cu2+, Zn2+, Cd2+, Hg2+, and Pb2+ was investigated by cyclic voltammetry (CV) in CH2Cl2/CH3CN 0.25:1 (v/v) mixture. Upon addition to L3 of increasing amounts of the aforementioned metal cations, the wave corresponding to the Fc+/Fc redox couple of the un-complexed L3 was gradually replaced by a new reversible wave at more positive potentials and corresponding to the Fc+/Fc redox couple of the complexed ligand. The maximum anodic shift of the ferrocene oxidation wave is observed in the presence of Pb2+ (230 mV), to which corresponds a reaction coupling efficiency (RCE) value as large as 7.9 × 103. The response selectivity of L3 is discussed in reference to the optical selectivity observed for conjugated chemosensors featuring L1 as receptor unit and different fluorogenic fragments as signalling units.

By studying the structures of (μ-1,4,10,13-tetrathia-7,16-diazacyclooctadecane)bis[iodidopalladium(II)] diiodide penta(diiodine), [Pd2I2(C12H26N2S4)](I)2·5I2 or [Pd2I2([18]aneN2S4)](I)2·(I2)5, and 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane triiodide iodide hemipenta(diiodine) dichloromethane monosolvate, C18H38N2O62+·I3-·I-·2.5I2·CH2Cl2 or [H2([2.2.2]cryptand)](I3)(I)(I2)2.5·CH2Cl2, we confirm the structural variety of extended polyiodides achievable upon changing the shape, charge and dimensions of the cation template, by altering the synthetic strategy adopted and/or the experimental conditions. Although it is still often difficult to characterize discrete [I2m+n]n- polyiodides higher than I3- on the basis of structural parameters, such as I-I bond distances, FT-Raman spectroscopy appears to identify them as aggregates of I2, I- and (symmetric or slightly asymmetric) I3- building blocks linked by I...I interactions of varying strengths. However, because FT-Raman spectroscopy carries no information about the topological features of extended polyiodides, the two techniques should therefore be applied in combination to enhance the analysis of this kind of compounds.

The article of Sommer [Acta Cryst. (2024), C80, 337-342] provides a concise and effective introduction to the subject of growing crystals suitable for structure determination.

Introducing the new Section Editor of Acta Crystallographica Section B.

Ruthenium complexes of phosphinocarboxamide ligands, and their use to form metallacycles using halide abstraction/deprotonation reactions are reported. Thus, [Ru(p-cym){PPh2C(=O)NHR}Cl2; R = iPr (1), Ph (2), p-tol (3)] and [Ru(p-cym){PPh2C(=O)N(R)C(=O)N(H)R}Cl2; R = Ph (4), p-tol (5)] were synthesized from [(p-cym)RuCl2]2 (p-cym = para-cymene) and phosphinocarboxamides or phosphinodicarboxamides, respectively. Single-crystal X-ray diffraction measurements on 1–5 reveal coordination to ruthenium through the phosphorus donor, with an intramolecular hydrogen bond between the amine-bound proton and a metal-bound chloride. Six-membered metallacycles formed by halide abstraction/deprotonation of complexes 4 and 5 afforded [Ru(p-cym){κ2-P,N-PPh2C(=O)N(R)C(=O)NR}Cl] [R = Ph (6), p-tol (7)]. These species exist as a mixture of two rotational isomers in solution, as demonstrated by NMR spectroscopy.

The nitrile-functionalized derivatives of 2,8-dithia-5-aza-2,6-pyridinophane ([12]anePyNS2)(Py = Pyridine), 1aza-4,7,10-trithiacyclododecane ([12]aneNS3), and N,N'-bis(2-pyridylmethyl)-propylenediamine (Pypn), referred to as L10, L11 and L12, respectively, have been prepared. Following the reaction of these ligands with silver(I) salts, the three coordination polymers (CPs) {[Ag(L10)](BF4)}& INFIN;, {[Ag(L11)](BF4)& BULL;1/2MeCN}& INFIN;, and {[Ag (L12)](NO3)}& INFIN;, have been isolated and structurally characterized. The structural features of the three CPs depends more on the nature of the un-functionalized ligands rather than on the presence of the nitrile groups. A comparative analysis of the structures of the three CPs is performed in relation to the structures of polymeric silver(I) compounds obtained with nitrile-functionalized pendant arms of related aza- and mixed donor macrocyclic ligands (L1-L9) reported in the literature.

The coordination chemistry towards silver(I) of the small-ring macrocycles [9]aneN2S (1-thia-4,7-diazacyclononane) and [9]aneNS2 (1,4-dithia-7-azacyclononane) incorporating nitrile-functionalized pendant arms is considered both in the presence and the absence of exogenous bridging ligands. The aim is to understand the influence of the number and length of the pendant arms on the nuclearity and dimensionality of the resulting complexes. The X-ray crystal structures of the complexes bis[4,7-bis(cyanomethyl)-1-thia-4,7-diazacyclononane-κ3N,N',S]silver(I) tetrafluoridoborate, [Ag(C10H16N4S)2]BF4 or [Ag(L1)2]BF4, [4,7-bis(2-cyanoethyl)-1-thia-4,7-diazacyclononane-κ3N,N',S](thiocyanato-κS)silver(I), [Ag(C12H20N4S)(NCS)] or [Ag(L2)(SCN)], and μ-thiocyanato-κ2S:S-bis{[7-(2-cyanoethyl)-1,4-dithia-7-azacyclononane-κ3N,S,S']silver(I)} tetrafluoridoborate, [Ag2(C9H16N2S2)2(SCN)]BF4 or [Ag2(L3)2(μ-SCN)]BF4, are discussed in relation to analogous compounds in the literature.

The desolvated (3,24)-connected metal-organic framework (MOF) material, MFM-160a, [Cu3(L)(H2O)3] [H6L = 1,3,5-triazine-2,4,6-tris(aminophenyl-4-isophthalic acid)], exhibits excellent high-pressure uptake of CO2 (110 wt% at 20 bar, 298 K) and highly selective separation of C2 hydrocarbons from CH4 at 1 bar pressure. Henry's law selectivities of 79:1 for C2H2:CH4 and 70:1 for C2H4:CH4 at 298 K are observed, consistent with ideal adsorption solution theory (IAST) predictions. Significantly, MFM-160a shows a selectivity of 16:1 for C2H2:CO2. Solid-state 2H NMR spectroscopic studies on partially deuterated MFM-160-d12 confirm an ultra-low barrier (∼2 kJ mol-1) to rotation of the phenyl group in the activated MOF and a rotation rate 5 orders of magnitude slower than usually observed for solid-state materials (1.4 × 106 Hz cf. 1011-1013 Hz). Upon introduction of CO2 or C2H2 into desolvated MFM-160a, this rate of rotation was found to increase with increasing gas pressure, a phenomenon attributed to the weakening of an intramolecular hydrogen bond in the triazine-containing linker upon gas binding. DFT calculations of binding energies and interactions of CO2 and C2H2 around the triazine core are entirely consistent with the 2H NMR spectroscopic observations.

Acta Crystallographica Section B launches a new section on crystal growth and actively welcomes submissions which match the scope of the journal.

We report the reversible adsorption of ammonia (NH3) up to 9.9 mmol g-1 in a robust Al-based metal-organic framework, MFM-303(Al), which is functionalized with free carboxylic acid and hydroxyl groups. The unique pore environment decorated with these acidic sites results in an exceptional packing density of NH3 at 293 K (0.801 g cm-3) comparable to that of solid NH3 at 193 K (0.817 g cm-3). In situ synchrotron X-ray diffraction and inelastic neutron scattering reveal the critical role of free -COOH and -OH groups in immobilizing NH3 molecules. Breakthrough experiments confirm the excellent performance of MFM-303(Al) for the capture of NH3 at low concentrations under both dry and wet conditions.

Photochemical synthesis of highly reactive hydroperoxides and their conversion into useful products, such as 1,2,4-trioxanes, are of wide interest for synthetic organic chemistry and pharmaceutical manufacturing particularly because of their relevance as potential antimalarial and anticancer treatment drugs, for example, Artemisinin. One class of antimalarial drugs is based on 1,2,4-trioxane scaffolds although production of such compounds on a gram scale is challenging due to their instability in oxidizable solvents. Furthermore, current methods employ either solid oxidants, which make continuous processing problematic, or molecular oxygen, requiring long reaction times of up to 48 h. Here, we report a new multigram continuous approach using a custom-built high-pressure sapphire photoreactor to synthesize trioxanes via the dearomatization of para-substituted phenols by photogenerated singlet oxygen in supercritical CO2. CO2 also facilitates mixing with O2 and has lower viscosity, thereby improving penetration into the pores of the solid acid catalyst used for the formation of trioxanes. We show the capabilities of a 5.2 mL reactor to scale up the reaction to 67 g/day. This synthetic approach provides a platform to rapidly access high-value compounds under flow conditions, with high atom efficiencies, excellent yields, short reaction times, and without the need for isolation of hazardous intermediates.

With an exceptional portfolio of properties such as high water content and cross-linked nature, hydrogels can provide an ideal and compatible environment not only to encapsulate but also to control the delivery of biological therapeutics. However, uncontrollable degradation, release and especially swelling impose limitations on our ability to engineer these gels. Herein a zirconium metallogel is proposed that utilizes zirconyl tetramers as the metal component in conjunction with a nucleic acid (adenine). The variable gel-formation temperature as a simple step of gel formation allows the tuning of gel formation and properties by controlling the adenine-nucleobase interactions. Reconstitution, entrapment, degradation, cytotoxicity, and release of bovine serum albumin (BSA) as a negatively charged macromolecular therapeutic agent were investigated. The controllable and sustained release of BSA, offers a route to new tailorable protein delivery applications.

This study investigates the coordination chemistry of the tetradentate pyridine-containing 12-membered macrocycles L1-L3 towards Platinum Group metal ions PdII, PtII, and RhIII. The reactions between the chloride salts of these metal ions and the three ligands in MeCN/H2O or MeOH/H2O (1:1 v/v) are shown, and the isolated solid compounds are characterized, where possible, by mass spectroscopy and 1H- and 13C-NMR spectroscopic measurements. Structural characterization of the 1:1 metal-to-ligand complexes [Pd(L1)Cl]2[Pd2Cl6], [Pt(L1)Cl](BF4), [Rh(L1)Cl2](PF6), and [Rh(L3)Cl2](BF4)·MeCN shows the coordinated macrocyclic ligands adopting a folded conformation, and occupying four coordination sites of a distorted square-based pyramidal and octahedral coordination environment for the PdII/PtII, and RhIII complexes, respectively. The remaining coordination site(s) are occupied by chlorido ligands. The reaction of L3 with PtCl2 in MeCN/H2O gave by serendipity the complex [Pt(L3)(m-1,3-MeCONH)PtCl(MeCN)](BF4)2·H2O, in which two metal centers are bridged by an amidate ligand at a Pt1-Pt2 distance of 2.5798(3) Å and feature one square-planar and one octahedral coordination environment. Density Functional Theory (DFT) calculations, which utilize the broken symmetry approach (DFT-BS), indicate a singlet d8-d8 PtII-PtII ground-state nature for this compound, rather than the alleged d9-d7 PtI-PtIII mixed-valence character reported for related dinuclear Pt-complexes.

The past decade has seen a diverse range of breakthrough inventions that are derived from gold complexes, including the application of aurophilic interactions in the preparation of stimuli-responsive materials. Examples of these gold-based materials include aurophilicity-induced metallogelators, mechanochromic, thermochromic, vapochromic, and solvatochromic luminescent compounds, as well as sensory materials for the detection of metal ions. Sophisticated properties of gold complexes with Au···Au contacts have been explored at the edge of several disciplines including chemistry, crystallography, molecular engineering and advanced materials. As science paves its way to innovation, cross-disciplinary research moves from being a luxury to becoming a necessity. Development of the concept of aurophilicity and its use in designing novel materials is a true example of innovation on a multidisciplinary platform. As miniaturization continues to influence the next generation of technological advancement, using the properties of molecules as chemical tools to enable such developments becomes extremely important. In this Review, recent examples of gold complexes which exhibit a response to external stimuli have been collected and some of their potential applications discussed for selected cases.

Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal which requires an understanding of the host-guest interactions involved at the atomic scale. Metal-organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a, Cu-1b, Cu-2), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a, the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO2 and CH4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO2 and CH4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal-organic framework (MOF) materials containing open metal sites increases their uptake of CO2. The results of the crystallographic study on MOP-gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a.

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 Ln ion to bind to donors. This ultimately leads to the construction of architectures with unique characteristics and applications. Within the great variety of functional groups, carboxylate type ligands are of interest in the construction of various architectures that not only depend on carboxylate coordination modes but are also influenced by their spatial arrangement. This study will concisely summarises the various architectures of Ce(III)-based CPs resulting from molecular self-assembly of Ce(III) and O/N-donor polydentate organic ligands. Furthermore, advanced applications of Ce(III)-based CPs in simultaneous luminescent sensing and detection of metal ions and radical organic species (ROS), and also the utilization of Ce(III)-based CPs as effective precursors for ceria (CeO2) are reviewed. This review covers research conducted on Ce(III)-based CPs after the year 2000. (C) 2020 Elsevier B.V. All rights reserved.

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 compound is best described as a nido metalla-group 13 cluster.

The synthesis and coordination properties of two fluorescent chemosensors, featuring [9]aneN3 (1,4,7-triazacyclononane; L1) and [12]aneNS3 (1-aza-4,7,10-trithiacyclododecane; L2) as receptor units, and a quinoline pendant arm with an amide group as a functional group spacer are described. The optical responses of L1 and L2 in the presence of several metal ions were analysed in MeCN/H2 O (1 : 4 v/v) solutions. A selective chelation enhancement of fluorescence (CHEF) effect was observed in the presence of Zn2+ in the case of L1, and in the presence of Cd2+ in the case of L2, following the formation of a 1 : 1 and a 1 : 2 metal/ligand complex, respectively, which was also confirmed by potentiometric measurements. 1 H and 13 C NMR measurements in CD3 CN/CDCl3 in combination with molecular mechanics calculations show that for both complexes of L1 and L2 with Zn2+ and Cd2+ , respectively, the coordination of the carbonyl group from the pendant arm could be the origin of the observed optical selectivity.