A diagnosis of environmental awareness in sport and sport policy

This article sheds light on the problematic, but urgent, relation between sport and its environmental effects by focusing on the development of internal policies in the Swedish sport movement as well as on external normative pressures for a sustainable environmental development. The materials in this study portray a passive (and blind) governance in relation to an official environmental policy at macro and meso levels, regardless of the manifestations of individual environmental projects in everyday sport practices. The analysis shows that the ideology of the autonomy of sport and the emphasis on self- regulation, regularly upheld by the Swedish Sports Confederation, is obsolete

From {Au^I···Au^I}‑Coupled Cages to the Cage-Built 2‑D {Au^I···Au^I} Arrays: Au^I···Au^I Bonding Interaction Driven Self-Assembly and Their Ag^I Sensing and Photo-Switchable Behavior

Metal–metal bonding interactions have been used to generate a number of unique supramolecular assemblies with fascinating functions. We presented here a new class of gold­(I)-containing metallosupramolecular cages and cage-built two-dimensional (2-D) arrays of {Au₈L₂}_<i>n</i> (<i>n</i> = 1 or ∞, L = tetrakis-dithiocarbamato-calix[4]­arene, TDCC), <b>1</b>–<b>3</b>, which are constructed from the self-assembly of deep-cavitand calix[4]­arene-based supramolecular cages consisting of octanuclear Au­(I) motifs. Synchrotron radiation X-ray diffraction structural analyses of <b>1</b>–<b>3</b> revealed their quadruple-stranded helicate dimeric cage structure and the presence of 2-D arrays of cages linked together by inter- and intramolecular Au^I···Au^I interactions. Electronic absorption and emission studies of complexes <b>1</b>–<b>3</b> indicated the occurrence of a programmable self-assembly process in a concentration-dependent stepwise manner with the links built via aurophilic interactions. These novel gold­(I) supramolecular cages exhibited green phosphorescence and have been shown to serve as highly selective proof-of-concept luminescent sensors toward Ag^I cation among various competitive transition-metal ions

From {Au^I···Au^I}‑Coupled Cages to the Cage-Built 2‑D {Au^I···Au^I} Arrays: Au^I···Au^I Bonding Interaction Driven Self-Assembly and Their Ag^I Sensing and Photo-Switchable Behavior

Metal–metal bonding interactions have been used to generate a number of unique supramolecular assemblies with fascinating functions. We presented here a new class of gold­(I)-containing metallosupramolecular cages and cage-built two-dimensional (2-D) arrays of {Au₈L₂}_<i>n</i> (<i>n</i> = 1 or ∞, L = tetrakis-dithiocarbamato-calix[4]­arene, TDCC), <b>1</b>–<b>3</b>, which are constructed from the self-assembly of deep-cavitand calix[4]­arene-based supramolecular cages consisting of octanuclear Au­(I) motifs. Synchrotron radiation X-ray diffraction structural analyses of <b>1</b>–<b>3</b> revealed their quadruple-stranded helicate dimeric cage structure and the presence of 2-D arrays of cages linked together by inter- and intramolecular Au^I···Au^I interactions. Electronic absorption and emission studies of complexes <b>1</b>–<b>3</b> indicated the occurrence of a programmable self-assembly process in a concentration-dependent stepwise manner with the links built via aurophilic interactions. These novel gold­(I) supramolecular cages exhibited green phosphorescence and have been shown to serve as highly selective proof-of-concept luminescent sensors toward Ag^I cation among various competitive transition-metal ions

From {Au^I···Au^I}‑Coupled Cages to the Cage-Built 2‑D {Au^I···Au^I} Arrays: Au^I···Au^I Bonding Interaction Driven Self-Assembly and Their Ag^I Sensing and Photo-Switchable Behavior

Metal–metal bonding interactions have been used to generate a number of unique supramolecular assemblies with fascinating functions. We presented here a new class of gold­(I)-containing metallosupramolecular cages and cage-built two-dimensional (2-D) arrays of {Au₈L₂}_<i>n</i> (<i>n</i> = 1 or ∞, L = tetrakis-dithiocarbamato-calix[4]­arene, TDCC), <b>1</b>–<b>3</b>, which are constructed from the self-assembly of deep-cavitand calix[4]­arene-based supramolecular cages consisting of octanuclear Au­(I) motifs. Synchrotron radiation X-ray diffraction structural analyses of <b>1</b>–<b>3</b> revealed their quadruple-stranded helicate dimeric cage structure and the presence of 2-D arrays of cages linked together by inter- and intramolecular Au^I···Au^I interactions. Electronic absorption and emission studies of complexes <b>1</b>–<b>3</b> indicated the occurrence of a programmable self-assembly process in a concentration-dependent stepwise manner with the links built via aurophilic interactions. These novel gold­(I) supramolecular cages exhibited green phosphorescence and have been shown to serve as highly selective proof-of-concept luminescent sensors toward Ag^I cation among various competitive transition-metal ions

Stereocontrolled Self-Assembly of Ln(III)–Pt(II) Heterometallic Cages with Temperature-Dependent Luminescence

Structurally well-defined discrete d/f heterometallic complexes show diverse application potential in electrooptic and magnetic materials. However, precise control of the component and topology of such heterometallic compounds with fine-tuned photophysical properties is still challenging. Herein, we report the stereocontrolled syntheses of a series of LnIII–PtII heterometallic cages through coordination-driven self-assembly of enantiopure alkynylplatinum-based metalloligands (L1R/S, L2R/S) with lanthanide ions (Ln = EuIII, YbIII, NdIII, LuIII). Taking advantage of the metal-to-ligand charge transfer (MLCT) excited state on the designed alkynylplatinum ligands, the excitation window for the sensitized near-infrared (NIR) luminescence on the YbIII- and NdIII-containing cages can be extended to the visible region (up to 500 nm). Linear temperature-dependent red and NIR emissions observed on the Ln4(L2R/S)6 (LnIII = EuIII and YbIII, respectively) complexes suggest their potential applications as luminescent temperature sensors, with sensitivities of −0.54% (LnIII = EuIII, 77–250 K) and −0.17% (LnIII = YbIII, 77–300 K) per K achieved. This work not only offers a good strategy to prepare new d/f heterometallic supramolecular cages but also paves the way for the design of stimuli-responsive luminescent materials

Hierarchical Self-Assembly and Chiroptical Studies of Luminescent 4d–4f Cages

Multinuclear lanthanide-containing supramolecular cages have received increasing attention recently because of their unique electroptical and magnetic properties. Here we report the hierarchical self-assembly and chiroptical studies of a group of 4d–4f heterometallic cages synthesized from a preformed dimetalloligand [(bpy)₂Pd₂<b>1</b>₂]²⁺ (<b>2</b>) (bpy = 2,2-bipyridine) and a variety of trivalent lanthanide ions (Ln = Nd^III, Eu^III, Yb^III). The programmable self-assembly process leading to the trigonal bipyramidal cages formulated as {Ln₂[(bpy)₂Pd₂<b>1</b>₂]₃}¹²⁺ (<b>3</b>) has been confirmed by one- and two-dimensional NMR, electro-spray-ionization time-of-flight mass-spectroscopy, and in one typical case by single-crystal X-ray diffraction studies. Circular dichroism and circular polarized luminescence spectra confirmed the strict control of stereoselectivity on the heterometallic cages, dictated by the chiral amide groups on the ligands. Excitation (up to 420 nm) on the dipalladium chromophores on these cages leads to the characteristic lanthanide luminescence at both the visible and the near-infrared regions, depending on the lanthanide ions used. Through the assembly–disassembly process, luminescent turn-off sensing toward penicillin among several widely used antibiotics has also been demonstrated with the Europium cage, featuring a limit of detection as low as 0.88 ppb (S/N = 3). Our results pave the way for the construction of chiral 4d–4f supramolecular cages which may find potential applications in luminescent sensing and/or labeling reagents

Evolution of Luminescent Supramolecular Lanthanide M_2<i>n</i>L_3<i>n</i> Complexes from Helicates and Tetrahedra to Cubes

Lanthanide-containing molecules have many potential applications in material science and biology, that is, luminescent sensing/labling, MRI, magnetic refrigeration, and catalysis among others. Coordination-directed self-assembly has shown great power in the designed construction of well-defined supramolecular systems. However, application of this strategy to the lanthanide edifices is challenging due to the complicated and greatly labile coordination numbers and geometries for lanthanides. Here we demonstrate a sensitive structural switching phenomenon during the stereocontrolled self-assembly of a group of Ln_2<i>n</i>L_3<i>n</i> (Ln for lanthanides, L for organic ligands, and <i>n</i> = 1, 2, 4) compounds. Systematic variation of the offset distances between the two chelating arms on the bis­(tridentate) ligands dictated the final outcomes of the lanthanide assembly, ranging from Ln₂L₃ helicates and Ln₄L₆ tetrahedra to Ln₈L₁₂ cubes. Remarkably, the borderline case leading to the formation of a mixture of the helicate and the tetrahedron was clearly revealed. Moreover, the concentration-dependent self-assembly of an unprecedented cubic Ln₈L₁₂ complex was also confirmed. The luminescent lanthanide cubes can serve as excellent turn-off sensors in explosives detection, featuring high selectivity and sensitivity toward picric acid. All complexes were confirmed by NMR, ESI-TOF-MS, and single crystal X-ray diffraction studies. Our results provide valuable design principles for the coordination self-assembly of multinuclear functional lanthanide architectures

Water-Soluble Redox-Active Cage Hosting Polyoxometalates for Selective Desulfurization Catalysis

Transformations within container-molecules provide a good alternative between traditional homogeneous and heterogeneous catalysis, as the containers themselves can be regarded as single molecular nanomicelles. We report here the designed-synthesis of a water-soluble redox-active supramolecular Pd₄L₂ cage and its application in the encapsulation of aromatic molecules and polyoxometalates (POMs) catalysts. Compared to the previous known Pd₆L₄ cage, our results show that replacement of two cis-blocked palladium corners with <i>p</i>-xylene bridges through pyridinium bonds formation between the 2,4,6-tri-4-pyridyl-1,3,5-triazine (TPT) ligands not only provides reversible redox-activities for the new Pd₄L₂ cage, but also realizes the expansion and subdivision of its internal cavity. An increased number of guests, including polyaromatics and POMs, can be accommodated inside the Pd₄L₂ cage. Moreover, both conversion and product selectivity (sulfoxide over sulfone) have also been much enhanced in the desulfurization reactions catalyzed by the POMs@Pd₄L₂ host–guest complexes. We expect that further photochromic or photoredox functions are possible taking advantage of this new generation of organo-palladium cage

Water-Soluble Redox-Active Cage Hosting Polyoxometalates for Selective Desulfurization Catalysis

Transformations within container-molecules provide a good alternative between traditional homogeneous and heterogeneous catalysis, as the containers themselves can be regarded as single molecular nanomicelles. We report here the designed-synthesis of a water-soluble redox-active supramolecular Pd₄L₂ cage and its application in the encapsulation of aromatic molecules and polyoxometalates (POMs) catalysts. Compared to the previous known Pd₆L₄ cage, our results show that replacement of two cis-blocked palladium corners with <i>p</i>-xylene bridges through pyridinium bonds formation between the 2,4,6-tri-4-pyridyl-1,3,5-triazine (TPT) ligands not only provides reversible redox-activities for the new Pd₄L₂ cage, but also realizes the expansion and subdivision of its internal cavity. An increased number of guests, including polyaromatics and POMs, can be accommodated inside the Pd₄L₂ cage. Moreover, both conversion and product selectivity (sulfoxide over sulfone) have also been much enhanced in the desulfurization reactions catalyzed by the POMs@Pd₄L₂ host–guest complexes. We expect that further photochromic or photoredox functions are possible taking advantage of this new generation of organo-palladium cage

Water-Soluble Redox-Active Cage Hosting Polyoxometalates for Selective Desulfurization Catalysis

Transformations within container-molecules provide a good alternative between traditional homogeneous and heterogeneous catalysis, as the containers themselves can be regarded as single molecular nanomicelles. We report here the designed-synthesis of a water-soluble redox-active supramolecular Pd₄L₂ cage and its application in the encapsulation of aromatic molecules and polyoxometalates (POMs) catalysts. Compared to the previous known Pd₆L₄ cage, our results show that replacement of two cis-blocked palladium corners with <i>p</i>-xylene bridges through pyridinium bonds formation between the 2,4,6-tri-4-pyridyl-1,3,5-triazine (TPT) ligands not only provides reversible redox-activities for the new Pd₄L₂ cage, but also realizes the expansion and subdivision of its internal cavity. An increased number of guests, including polyaromatics and POMs, can be accommodated inside the Pd₄L₂ cage. Moreover, both conversion and product selectivity (sulfoxide over sulfone) have also been much enhanced in the desulfurization reactions catalyzed by the POMs@Pd₄L₂ host–guest complexes. We expect that further photochromic or photoredox functions are possible taking advantage of this new generation of organo-palladium cage