A Three-Dimensional Dynamic Supramolecular "Sticky Fingers" Organic Framework.

Engineering high-recognition host-guest materials is a burgeoning area in basic and applied research. The challenge of exploring novel porous materials with advanced functionalities prompted us to develop dynamic crystalline structures promoted by soft interactions. The first example of a pure molecular dynamic crystalline framework is demonstrated, which is held together by means of weak "sticky fingers" van der Waals interactions. The presented organic-fullerene-based material exhibits a non-porous dynamic crystalline structure capable of undergoing single-crystal-to-single-crystal reactions. Exposure to hydrazine vapors induces structural and chemical changes that manifest as toposelective hydrogenation of alternating rings on the surface of the [60]fullerene. Control experiments confirm that the same reaction does not occur when performed in solution. Easy-to-detect changes in the macroscopic properties of the sample suggest utility as molecular sensors or energy-storage materials

Synthesis and Structural Characterization of a Series of One-Dimensional Heteronuclear Dirhodium-Silver Coordination Polymers

Herein, we describe the preparation of heteronuclear dirhodium-silver complexes by reaction between molecular Rh(II)-Rh(II) compounds [Rh2(μ-O2CR)4L2] (R = Me, Ph (1), CH2OEt (2); L = solvent molecules) with paddlewheel structure and PPh4[Ag(CN)2]. One-dimensional coordination polymers of (PPh4)n[Rh2(μ-O2CR)4Ag(CN)2]n (R = Me (3), Ph (4), CH2OEt (5)) formula have been obtained by replacement of the two labile molecules in the axial positions of the paddlewheel structures by a [Ag(CN)2]− bridging unit. The crystal structures of 3–5 display a similar arrangement, having anionic chains with a wavy structure and bulky (PPh4)+ cations placed between the chains. The presence of the (PPh4)+ cations hinders the existence of intermolecular Ag-Ag interactions although several C-H····π interactions have been observed. A similar reaction between [Rh2(μ-O2CCMe3)4(HO2CCMe3)2] and PPh4[Ag(CN)2] led to the molecular compound (PPh4)2{Rh2(μ-O2CCMe3)4[Ag(CN)2]2} (6) by replacement of the axial HO2CCMe3 ligands by two [Ag(CN)2]− units. The trimethylacetate ligand increases the solubility of the complex during the crystallization favouring the formation of discrete heteronuclear species

Heteronuclear Dirhodium-Gold Anionic Complexes: Polymeric Chains and Discrete Units

In this article, we report on the synthesis and characterization of the tetracarboxylatodirhodium(II) complexes [Rh2(μ–O2CCH2OMe)4(THF)2] (1) and [Rh2(μ–O2CC6H4–p–CMe3)4(OH2)2] (2) by metathesis reaction of [Rh2(μ–O2CMe)4] with the corresponding ligand acting also as the reaction solvent. The reaction of the corresponding tetracarboxylato precursor, [Rh2(μ–O2CR)4], with PPh4[Au(CN)2] at room temperature, yielded the one-dimensional polymers (PPh4)n[Rh2(μ–O2CR)4Au(CN)2]n (R = Me (3), CH2OMe (4), CH2OEt (5)) and the non-polymeric compounds (PPh4)2{Rh2(μ–O2CR)4[Au(CN)2]2} (R = CMe3 (6), C6H4–p–CMe3 (7)). The structural characterization of 1, 3·2CH2Cl2, 4·3CH2Cl2, 5, 6, and 7·2OCMe2 is also provided with a detailed description of their crystal structures and intermolecular interactions. The polymeric compounds 3·2CH2Cl2, 4·3CH2Cl2, and 5 show wavy chains with Rh–Au–Rh and Rh–N–C angles in the ranges 177.18°–178.69° and 163.0°–170.4°, respectively. A comparative study with related rhodium-silver complexes previously reported indicates no significant influence of the gold or silver atoms in the solid-state arrangement of these kinds of complexes

A switchable iron-based coordination polymer toward reversible acetonitrile electro-optical readout.

Efficient and low cost detection of harmful volatile organic compounds (VOCs) is a major health and environmental need in industrialized societies. For this, tailor-made porous coordination polymers are emerging as promising molecular sensing materials thanks to their responsivity to a wide variety of external stimuli and could be used to complement conventional sensors. Here, a non-porous crystalline 1D Fe(ii) coordination polymer acting as a porous acetonitrile host is presented. The desorption of interstitial acetonitrile is accompanied by magneto-structural transitions easily detectable in the optical and electronic properties of the material. This structural switch and therefore its (opto)electronic readout are reversible under exposure of the crystal to acetonitrile vapor. This simple and robust iron-based coordination polymer could be ideally suited for the construction of multifunctional sensor devices for volatile acetonitrile and potentially for other organic compounds

A robust and unique iron(ii) mosaic-like MOF

A novel extended triazole-based ligand (PM-Tria) has been synthesized and an unprecedented MOF 3D has serendipitously been formed by assembling iron(II), PM-Tria ligand and fluoride anions. This MOF contains a perfectly linear one-dimensional {Fe(II)–F}n bridging chain that shows an antiferromagnetic behaviour. Furthermore, the structure is compared with a 14th century mosaic found in the Alhambra Palace in Granada showing a surprising symmetry resemblance

A robust and unique iron(II) mosaic-like MOF

A novel extended triazole-based ligand (PM-Tria) has been synthe- sized and an unprecedented MOF 3D has serendipitously been formed by assembling iron(II), PM-Tria ligand and fluoride anions. This MOF contains a perfectly linear one-dimensional {Fe(II)–F}n bridging chain that shows an antiferromagnetic behaviour. Further- more, the structure is compared with a 14th century mosaic found in the Alhambra Palace in Granada showing a surprising symmetry resemblance

Divergent Adsorption-Dependent Luminescence of Amino- Functionalized Lanthanide Metal-Organic Frameworks for Highly Sensitive NO2 Sensors

A novel gas sensing mechanism exploiting the luminescence modulation upon NO2 adsorption is here demonstrated. Two isostructural lanthanide based-metal-organic frameworks are used including a recognition center (aminogroup) that provides high selectivity for NO2 molecules. Energy transfer from the organic ligands to Ln is strongly dependent on the presence of NO2, resulting in an unprecedented photoluminescent sensing scheme. Thereby, NO2 exposition triggers either a reversible enhancement or a decrease of the luminescence intensity, depending on the lanthanide ion (Eu or Tb). Our experimental studies combined with DFT and complete active space self-consistent field calculations, provide understanding of the nature and effects of NO2 interactions within the MOFs and the signal transduction mechanism.<br /

Divergent Adsorption-Dependent Luminescence of Amino-Functionalized Lanthanide Metal–Organic Frameworks for Highly Sensitive NO 2 Sensors

International audienceA novel gas sensing mechanism exploiting lanthanide luminescence modulation upon NO2 adsorption is demonstrated here. Two isostructural lanthanide-based metal–organic frameworks (MOFs) are used, including an amino group as the sensitive recognition center for NO2 molecules. The transfer of energy from the organic ligands to Ln is strongly dependent on the presence of NO2, resulting in an unprecedented photoluminescent sensing scheme. Thereby, NO2 exposition triggers either a reversible enhancement or a decrease in the luminescence intensity, depending on the lanthanide ion (Eu or Tb). Our experimental studies combined with density functional theory and complete active space self-consistent field calculations provide an understanding of the nature and effects of NO2 interactions within the MOFs and the signal transduction mechanism

Global attitudes in the management of acute appendicitis during COVID-19 pandemic: ACIE Appy Study

Background: Surgical strategies are being adapted to face the COVID-19 pandemic. Recommendations on the management of acute appendicitis have been based on expert opinion, but very little evidence is available. This study addressed that dearth with a snapshot of worldwide approaches to appendicitis. Methods: The Association of Italian Surgeons in Europe designed an online survey to assess the current attitude of surgeons globally regarding the management of patients with acute appendicitis during the pandemic. Questions were divided into baseline information, hospital organization and screening, personal protective equipment, management and surgical approach, and patient presentation before versus during the pandemic. Results: Of 744 answers, 709 (from 66 countries) were complete and were included in the analysis. Most hospitals were treating both patients with and those without COVID. There was variation in screening indications and modality used, with chest X-ray plus molecular testing (PCR) being the commonest (19\ub78 per cent). Conservative management of complicated and uncomplicated appendicitis was used by 6\ub76 and 2\ub74 per cent respectively before, but 23\ub77 and 5\ub73 per cent, during the pandemic (both P < 0\ub7001). One-third changed their approach from laparoscopic to open surgery owing to the popular (but evidence-lacking) advice from expert groups during the initial phase of the pandemic. No agreement on how to filter surgical smoke plume during laparoscopy was identified. There was an overall reduction in the number of patients admitted with appendicitis and one-third felt that patients who did present had more severe appendicitis than they usually observe. Conclusion: Conservative management of mild appendicitis has been possible during the pandemic. The fact that some surgeons switched to open appendicectomy may reflect the poor guidelines that emanated in the early phase of SARS-CoV-2