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A series of bis -acryl functionalized porphyrins and their corresponding metalloporphyrins (M = Co, Mn) were synthesized and investigated for their antimicrobial properties through MIC screening and bacteria time-kill kinetic studies. The Mn(III) 4-(bis)methylphenyl-substituted-porphyrins showed superior batericidal activities even in the dark with low hemotoxicity and good cytotoxicity profile.

A series of triangular metallaprisms with a kinetically inert Pt-N bond have been synthesized from the stepwise assembly of a Pt-corner, linear linker 4,4'-bipy (4,4'-bipy = 4,4'-bipyridine) and triangular ligand [tpb or tpt, tpb = tris(4-pyridyl)benzene, tpt = tris(4-pyridyl)triazine]. The use of an unsymmetrical [Pt(HL)]-corner (H

The frontispiece shows a novel in situ method of generating metal nanoparticles within porous molecular frameworks, thereby affording highly active and selective single-site heterogeneous catalysts for industrially significant aerobic oxidations. The Communication on page 1226 by Robert Raja and Andy Hor et al. highlights the importance of spectroscopic and kinetic studies in establishing structureproperty correlations that are fundamental in the design of sustainable heterogeneous catalysts.

Two Zn-based metal–organic frameworks (MOFs) of pyridinemethanol–carboxylate conjugated ligands, namely, [Zn(L1)]n xSol (1, 3D) and [Zn(L2)2]n (2, 1D) (H2L1 = 4-(6-(hydroxymethyl)pyridin-3-yl)benzoic acid; H2L2 = 3-(6-(hydroxymethyl)pyridin-3-yl)benzoic acid) have been synthesized and structurally characterized. The dimensionalities of 1 and 2 are defined by the deprotonation states of the ligands. Specifically, the 3D MOF 1 features a rod-shaped Zn–O/COO chain as the secondary building unit (SBU) which effectively hinder network interpenetration, whereas the 1D chain of 2 mimics an edge-sharing octahedron with each Zn center serving as the vertex. MOF 1 reversibly uptakes CO2 and exhibits a Brunauer–Emmett–Teller (BET) surface of 345 m2 g−1, and remains crystalline upon activation, an indication of permanent porosity.

The catalytic activity of iron(II) complexes with functionalized amine-pyrazolyl tripodal ligands toward dimerization of terminal alkynes in the presence a base (KOtBu or NaOtBu) has been studied. An unusual E/Z selectivity of the reaction determined by tert-butoxide was observed.

Two complexes, [Cu6I6(L1)3]n (I) and [Cu4I4(L2)2]n (II) (L1 = 1,4-bis(phenylthio)but-2-yne; L2 = 1,4-bis(phenylthio)butane), as precursors for thermoelectric composites were prepared using a literature procedure. During the preparation of I, an unexpected 3-D polymorph [Cu4I4(L1)2]n (1) with a triclinic space group and an infinite [CuI]n staircase structure was obtained. This new polymorph (1) exhibited the same structure at both room temperature and 173 K. Complexes 1 and II were therefore pyrolysed to composites 2 and 3, respectively, at 400 °C under a nitrogen gas flow. Composite 3 was pale in color with a low carbon content (0.05 wt%) and easily disassembled during handling. By comparison, the high carbon containing (10.2 wt%) composite 2 can be compressed into a robust, light pellet (density 3.58 g cm-3), which showed a moderate to high Seebeck coefficient (543-1308 μV K-1) over the temperature range 70-240 °C.

Coordination polymer 1 was prepared from CuI and a flexible [SNS] ligand L in acetonitrile. The thermal decomposition of 1 yielded a CuI-rich thermoelectric carbon composite 2, which is relatively light, thermally stable and robust. Composite 2 possesses high Seebeck coefficients (700-950 μV K-1) from rt to 204 °C after an optimization cycle.

[L2Cu4I4]n (1) based on a cubic [Cu4I4] node and ditopic, bridging bis(triazole) (L = 2,6-bis((1H-1,2,3-triazol-1-yl)methyl)pyridine) is a unique and highly symmetric cubane cluster based coordination polymer with strong yellow emission. Comparison with similar coordination polymers permits a structure activity relationship and reveals that the emission energy for these [Cu4I4] cluster-based materials occurs in the mid-range of Cu⋅⋅⋅Cu distances and tetrahedral geometry index values.

Molecular architectures containing photosensitive units respond to light, giving dramatic variations of their structure. In particular, the crystalline packing phases offer the possibility of significant advances in crystal design and the understanding of solid-state photoreactivity. In this review we mainly focus on three different photoreactivity patterns, namely the isomerization of azobenzene, open-ring↔closed-ring transformations of diarylethenes and cycloadditions of olefin pairs, as well as some examples of photoreactive crystals outside these types. Many interesting phototriggered functionalities are documented herein, such as photo-tuning of guest adsorption of azobenzene or diarylethene-based porous frameworks and crystalline organic polymers generated by photo-cycloaddition reactions taking place in the different networks.

Interlocked molecules are a type of supramolecules whose sub-components are held together not by covalent bonds but non-covalent interactions. Examples include rotaxanes, catenanes, Solomon links, ring-in-ring complexes, molecular Borromean rings, molecular knots and interlocked cages. The design and manufacture of these architectures is mainly based on self-assembly and template-directed methodologies. Inspired by the successful utilization of coordination-driven assembly in metallasupramolecular systems, the metallacyclic assembly of interlocked superstructures is developing rapidly and as such makes a fascinating topic for reviewing. In this review we will focus on the metal-directed synthesis of the different types of interlocked superstructures, as well as their functional applications.

We report Ni/NiOx nanoparticle-decorated carbon nanofibers, produced via electrospinning with subsequent heat treatments, as efficient oxygen evolution reaction catalysts for rechargeable Zn–air batteries with superior performances.

Advanced batteries with long cycle life and capable of harnessing more energies from multiple electrochemical reactions are both fundamentally interesting and practically attractive. Herein, we report a robust hybrid zinc-battery that makes use of transition-metal-based redox reaction (M–O–OH → M–O, M = Ni and Co) and oxygen reduction reaction (ORR) to deliver more electrochemical energies of comparably higher voltage with much longer cycle life. The hybrid battery was constructed using an integrated electrode of NiCo2O4 nanowire arrays grown on carbon-coated nickel foam, coupled with a zinc plate anode in alkaline electrolyte. Benefitted from the M–O/M–O–OH redox reactions and rich ORR active sites in NiCo2O4, the battery has concurrently exhibited high working voltage (by M–O–OH → M–O) and high energy density (by ORR). The good oxygen evolution reaction (OER) activity of the electrode and the reversible M–O ↔ M–O–OH reactions also enabled smooth recharging of the batteries, leading to excellent cycling ...

Neutral chloride-based electrolyte and directly grown manganese oxide on carbon paper are used as the electrolyte and air cathode respectively for rechargeable Zn-air batteries. Oxygen reduction and oxygen evolution reactions on manganese oxide show dependence of activities on the pH of the electrolyte. Zn-air batteries with chloride-based electrolyte and manganese oxide catalyst exhibit satisfactory voltage profile (discharge and charge voltage of 1 and 2 V at 1 mA cm−2) and excellent cycling stability (≈90 days of continuous cycle test), which is attributed to the reduced carbon corrosion on the air cathode and decreased carbonation in neutral electrolyte. This work describes a robust electrolyte system that improves the cycle life of rechargeable Zn-air batteries.

The oxygen reduction reaction (ORR) is traditionally catalyzed by carbon-supported precious metals, heteroatom-doped carbons, and transition-metal–carbon hybrids. Despite their good electric conductivity and high catalytic activities, these carbon-containing catalysts suffer from electrochemical carbon corrosion which limits their utility in metal–air batteries and fuel cells. Here, we report a class of perovskite La0.5Sr0.5Mn1–xNixO3−δ nanocrystals that are intrinsically conductive with good electrocatalytic activity for the ORR. Among these perovskites, La0.5Sr0.5Mn0.9Ni0.1O3−δ (δ = 0.06, LSMN) exhibited the highest electrocatalytic activity for ORR with an onset potential of 1.02 V, a half-wave potential of 0.80 V, and a Tafel slope of −68 mV decade–1 in 0.1 M potassium hydroxide aqueous solution. Negligible degradation of oxygen reduction currents was observed after 300 cyclic voltammetry scans from 1.08 to 0.15 V. We demonstrated that the electrically conductive perovskites with transition-metal redo...

Re(I) carbonyl complexes containing pyridyl-imine or amine ligands have been synthesized and crystallographically characterized. Their catalytic activity for the cis-cyclooctene epoxidation with tert-butyl hydroperoxide (TBHP) as oxidant and the oxidation of these Re(I) complexes by TBHP have been investigated.

Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO2 utilizing pinacolborane at r.t. and 1 atm CO2, with the combination of [Ru(CNCBn)(CO)2(H)][PF6] and KOCO2tBu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

Transition metal and nitrogen co-doping into carbon is an effective approach to promote the catalytic activities towards the oxygen reduction reaction (ORR) and/or oxygen evolution reaction (OER) in the resultant electrocatalysts, M/N-C. The preparation of such catalysts, however, is often complicated and in low yield. Herein we report a robust approach for easy synthesis of M/N-C hybrids in high yield, which includes a mussel-inspired polymerization reaction at room temperature and a subsequent carbonization process. With the introduction of selected transition metal salts into an aqueous solution of dopamine (DA), the obtained mixture self-polymerizes to form metal-containing polydopamine (M-PDA) composites, e.g. Co-PDA, Ni-PDA and Fe-PDA. Upon carbonization at elevated temperatures, these metal-containing composites were converted into M/N-C, i.e. Co-PDA-C, Ni-PDA-C and Fe-PDA-C, respectively, whose morphologies, chemical compositions, and electrochemical performances were fully studied. Enhanced ORR activities were found in all the obtained hybrids, with Co-PDA-C standing out as the most promising catalyst with excellent stability and catalytic activities towards both ORR and OER. This was further proven in Zn-air batteries (ZnABs) in terms of discharge voltage stability and cycling performance. At a discharge-charge current density of 2 mA cm(-2) and 1 h per cycle, the Co-PDA-C based ZnABs were able to steadily cycle up to 500 cycles with only a small increase in the discharge-charge voltage gap which notably outperformed Pt/C; at a discharge current density of 5 mA cm(-2), the battery continuously discharged for more than 540 h with the discharge voltage above 1 V and a voltage drop rate of merely 0.37 mV h(-1). With the simplicity and scalability of the synthetic approach and remarkable battery performances, the Co-PDA-C hybrid catalyst is anticipated to play an important role in practical ZnABs.

A generic catch–release catalysis system has been designed for the recovery of homogeneous catalysts at the end of a reaction using host–guest interactions. This proof-of-concept system consists of a palladium(II)–dipyrazole complex bearing an adamantyl (Ad) molecular recognition moiety (guest), and magnetic nanoparticles (MNP) decorated with β-cyclodextrins (β-CD) (host). The density of β-CD on the iron oxide nanoparticles was up to 3.1 × 10−4 mmol per mg, sufficient to efficiently catch the Ad-adorned Pd catalyst in aqueous methanol at room temperature. Release and recycling of the catalyst was achieved by extraction with methanol. This catch–release system performed well in the Suzuki–Miyaura coupling, but suffers from slow degradation which restricts the number of times that the catalyst and magnetic nanoparticles can be recycled and reused.

Solvothermal synthesis of Cu2O cubes from Cu(OAc)2 in ethanol provided templates for tunable formation of novel multicomponent composites: hollow CeO2-Cu2O (), core-shell NiO@Cu2O () and hollow CeO2-NiO-Cu2O (). Composites catalyze the oxidation of CO at a lower temperature than the parent Cu2O cubes.

Polymorphic compounds {[Cu(dcbb)2(H2O)2]·10H2O}n (2, 1D chain), [Cu(dcbb)2]n (3, 2D layer) and their co-crystal {[Cu(dcbb)2(H2O)][Cu(dcbb)2]2}n (4) have been prepared from the coordination reaction of a 2D polymer [Na(dcbb)(H2O)]n (1, H2dcbbBr = 1-(3,5-dicarboxybenzyl)-4,4'-bipyridinium bromide) with Cu(NO3)2·3H2O at different temperatures in water. Compounds 2-4 have an identical metal-to-ligand stoichiometric ratio of 1 : 2, but absolutely differ in structure. Compound 3 features a 2D layer structure with aromatic rings, positively charged pyridinium and free carboxylates on its surface, promoting electrostatic, π-stacking and/or hydrogen-bonding interactions with the carboxyfluorescein (FAM) labeled probe single-stranded DNA (probe ss-DNA, delineates as P-DNA). The resultant P-DNA@3 system facilitated fluorescence quenching of FAM via a photoinduced electron transfer process. The P-DNA@3 system functions as an efficient fluorescent sensor selective for HIV double-stranded DNA (HIV ds-DNA) due to the formation of a rigid triplex structure with the recovery of FAM fluorescence. The system reported herein also distinguishes complementary HIV ds-DNA from mismatched target DNA sequences with the detection limit of 1.42 nM.

Cyclopentadienyl (Cp) Ni(II) complexes [CpNiL][PF6] containing hybrid N,C chelating benzothiazolyl NHC ligands (L1 = 1-(2-benzothiazolyl)-3-methylimidazol-2-ylidene, 3a; L2 = 1-(2-benzothiazolyl)-3-allylimidazol-2-ylidene, 3b; L3 = 1-(2-benzothiazolyl)-3-benzylimidazol-2-ylidene, 3c) have been synthesized and fully characterized. The catalytic activity of 3a–3c in some C–C bond formation reactions has been examined. They are efficient catalysts for the homo-coupling of benzyl bromide in the presence of MeMgCl at r.t. with good functional group tolerance. Complex 3a is active in the catalytic oxidative homo-coupling of Grignard reagents with 1,2-dichloroethane as an oxidant at r.t.

A ligand-accelerated effect is observed in the cyclization of propargylic amides catalyzed by bis(pyridyl)silver(I) complexes, with an unexpected reversal of electronic demand to the analogous NH addition reaction. The catalyst was found to be effective for internal alkyne substrates, offering exclusive selectivity for the 5-exo-dig product. Differences in selectivity profile between gold- and silver-catalyzed processes are highlighted and discussed.

The stereospecific intramolecular hydroamination of alkynyl trichloroacetimidates catalyzed by bis(pyridyl)silver(I) complexes to form 1,3-oxazolines and oxazines has been investigated in greater detail. The rate of the reaction is profoundly influenced by the electronic character of the pyridyl ligand; leading to optimized conditions whereby reactions can be completed at ambient temperature with catalyst loadings as low as 1 mol%, while maintaining stereoselectivity towards the (Z)-isomer. Further investigations into establishing the role of the ligand, and the synthesis of (E)-isomer, are also presented.

The oxygen reduction reaction (ORR) is an important electrode reaction for energy storage and conversion devices based on oxygen electrocatalysis. This paper introduces the thermodynamics, reaction kinetics, reaction mechanisms, and reaction pathways of ORR in aqueous alkaline media. Recent advances of the catalysts for ORR were extensively reviewed, including precious metals, nonmetal-doped carbon, carbon–transition metal hybrids, transition metal oxides with spinel and perovskite structures, and so forth. The applications of those ORR catalysts to zinc–air batteries and alkaline fuel cells were briefly introduced. A concluding remark summarizes the current status of the reaction pathways, advanced catalysts, and the future challenges of the research and development of ORR.

The dinuclear complex [Cu2 I2 (L1)2 ] (1) (L1=3-((4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)methyl)benzonitrile) is characterized by single-crystal X-ray diffraction (XRD), powder XRD, IR, photoluminescence spectroscopy, and thermogravimetric analysis. Unlike other related, known copper iodide complexes, it exhibits strong yellow emission in the solid state at both room temperature and 77 K. Showing good compatibility with PMMA, it is blended with the polymer in different weight ratios to prepare luminescent composite fibers.

With new chemistry and advantageous configuration, the lithium-oxygen (Li-O2) battery promises a much higher specific energy than traditional lithium-ion batteries. The limited understanding on the complicated battery reactions therein, however, has become a major bottleneck of its development for applications requiring a high energy efficiency and long cycle-life. Herein, in a confined potential window with negligible electrolyte degradation, we studied the rechargeability of Li-O2 cathodes with pre-filled well-defined discharge products of Li2O2, Li2CO3, LiOH, or their combinations. Our results suggest Li2CO3 as the most difficult species to be electrochemically decomposed among the three lithium compounds, whereas the presence of LiOH notably increases the initial charge potential. The clearly visible difference in the charge behavior and cycling stability of these artificially "discharged" electrodes provides a guideline for the development of future high-performance Li-O2 batteries.

Across the periodic table, Group 6 metals (Cr, Mo, W) play an important role in the development of carbene chemistry. In this review, we highlight the synthetic methodologies, structures, reactivities and functions of about 500 N-heterocyclic carbene (NHC) complexes of these metals reported in the last four decades. Some emerging trends and applications are also summarized.

Four porous coordination networks have been synthesized from 1,4-benzenedicarboxylate with Cl, Br, I, and NO2 substituents whose different spatial differences are sufficient to influence the coordination mode of adjacent carboxyl moieties to unlock an inter-penetrating framework to give isostructural structures. Their size and polarity differences account for the diverging CO2 adsorption performances.

The addition of pyridine-3-carboxylic acid (3-PyCOOH), (E)-3-(pyridin-3-yl)acrylic acid (3-PyCH=CHCOOH), or 3-(pyridin-4-yl)benzoic acid (3-PyPhCOOH) to the Lewis acidic [Cu(dppf)(NCMe)2][BF4]·2MeCN·2H2O [1·2MeCN·2H2O, dppf = 1,1′-bis(diphenylphosphanyl)ferrocene] in the presence of NEt3 afforded the complexes [Cu2(dppf)2(3-PyCOO)2]·3CHCl3 (2·3CHCl3), [Cu2(dppf)2(3-PyCH=CHCOO)2]·CH2Cl2·C6H14 (3·CH2Cl2·C6H14), and [Cu2(dppf)2(3-PyPhCOO)2]·CH2Cl2 (4·CH2Cl2) with a common metallomacrocycle core and doubly bridging pyridine–carboxylate ligands as spacers. These dinuclear complexes have been structurally characterized by single-crystal X-ray crystallography, and their emission activities have been studied.

Bifunctional electrocatalysts for rechargeable metal–air batteries often encounter catalyst leaching-resultant performance degradation upon cycling of the batteries, which requires an improvement in stability of the catalyst nanoparticles via immobilization onto conductive supports. Herein, we report in situ growth of Co3O4 nanoparticles onto concurrently synthesized N-doped Vulcan carbon (NVC) to produce Co3O4/NVC powders with tuneable loading density as scalable, stable and efficient hybrid bifunctional electrocatalysts. With an optimized composition the hybrid catalyst exhibited satisfactory ORR and OER activity, giving a voltage difference as small as 0.10 V between the onset potential and half-wave potential at discharge. The good performance of the rechargeable zinc–air batteries constructed using Co3O4/NVC as air-cathodes suggests such a hybrid bifunctional electrocatalyst is a practical and cost-effective solution for applications which demand a large quantity of materials, e.g. in grid-scale energy storage and electric vehicles.

Zwitterionic 3d metal carboxylates of Zn(II), Cu(II), Ni(II) and Co(II) have been isolated and structurally authenticated by X-ray crystallography. A series of 2-hydroxymethylpyridine-carboxylate ligands with different sizes and shapes demonstrate variable coordination modes with first row transition metals under different conditions, yielding a class of 17 complexes, predominantly zwitterions. The nature of the ligands permits the carboxylates to be un-coordinated, anionic and conjugated, thereby balancing the positive charges on the metal centers.

A microporous hydrogen-bonded organic framework (HOF) derived from a polyhedral oligomeric silsesquioxane (POSS) intermediate and an aggregation-induced emission (AIE) luminogen tetraphenylethene (TPE) derivative has been synthesized and structurally characterized by various methods. This unique HOF exhibits a permanent porosity with a Brunauer–Emmett–Teller (BET) surface area of 101.9 m2 g−1. This HOF could be well dispersed in organic solvents in the form of nanoparticles with a size of a few hundred nanometers. These nanoparticles are highly fluorescent in organic solution, and exhibit a high fluorescence quenching selectivity towards copper ions. Furthermore, the fluorescence of this HOF could be recovered by the removal of copper ions upon addition of cyanide and, more interestingly, this process could be repeated several times without considerably sacrificing the sensing activity towards copper ions.

Four Au-(μ-phosphinite)-In units assemble to form an unprecedented Au2In2 12-membered metallacycle which intersects at the In centres an 8-membered ring containing two In-μ-phosphinate linkages, resulting in a tricyclic structure. Thermal treatment of this complex and of its Ag(I) analog affords Au-In-P and Ag-In-P nanomaterials, respectively.

A series of Mo(0) and W(0) carbonyl N-heterocyclic carbene (NHC) complexes containing monodentate NHC ligands with the formulae of M(CO)4(NHC)2 (NHC = IBz = 1,3-dibenzylimidazol-2-ylidene, M = Mo (1a), W (2a); NHC = InPr = 1,3-dipropylimidazol-2-ylidene, M = Mo (3), W (4a)) and M(CO)5(NHC) (NHC = IBz, M = Mo (1b), W (2b); NHC = InPr, M = W (4b); NHC = IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, M = Mo (5), W (6)) and the complexes containing chelating NHC ligands Mo(CO)4(PyNHC) (PyNHC = 3-methyl-1-picolylimidazol-2-ylidene (7)) and Mo(CO)3(Py2NHC) (Py2NHC = 1,3-dipicolylimidazol-2-ylidene (8)) have been synthesized and fully characterized. They show moderate catalytic activities towards cyclooctene epoxidation in the presence of tert-butyl hydroperoxide (TBHP). The stability of Mo–CNHC bond under oxidative condition has been investigated.

Extensive research and development on theoretical calculation and synthetic methods over the past few years have made doped graphene one of the most promising candidates for metal-free oxygen reduction reaction (ORR) catalysts. However, from the performance point of view, there is still a long way to go for these doped graphene-based catalysts to meet the requirements needed for commercial applications. What is the key to further improve the catalytic activity of doped graphene toward ORR to make them commercially viable? In this review, we will try to answer this question by fundamentally giving a detailed analysis based on the theoretical calculations to reveal the origin of ORR activity of doped graphene and the structure–performance relationship of such materials. Thereafter, we will provide an overview on the recent advances in the catalytic activity improvement of doped graphene, including major works using approaches of increasing the number of active sites, controlling the doping types (particularly for nitrogen doped graphene), developing co-doped graphene, and extending the surface area of doped graphene. Finally, in this perspective, we discuss some development opportunities and pathways that can lead to more efficient doped-graphene based ORR electrocatalysts approaching the practical use for fuel cells and metal–air batteries.

We report for the first time a novel method to synthesize sulfur–carbon yolk–shell particles with sulfur fully confined inside the conductive carbon shells, and the filling content of sulfur can be well-controlled and fine-tuned. In the yolk–shell structure the sulfur spheres partially occupy the internal void space of highly conductive carbon, allowing for comfortable accommodation of the volume expansion of sulfur upon lithiation during the battery discharge process. 3D interconnected nanostructures based on such sulfur–carbon yolk–shell particles exhibit a high initial capacity of 560 mA h g−1 (per gram electrode) with good cycling performance, promising high potential in rechargeable lithium–sulfur batteries for a wide range of applications.

We report 2D microporous carbon sheets with high surface area, derived from eggplant via simple carbonization and KOH activation, as low cost yet efficient bifunctional catalysts for high performance rechargeable zinc-air batteries.

We report a facile, one-step green synthesis of two new star-shaped compounds containing three or six pendant carbonate groups with terminal alkynes. The reaction occurs under 1 atm CO2 and proceeds optimally at room temperature. These multialkynyl-carbonate-functionalized benzenes represent readily accessible precursors to more complex dendritic materials.

We report cobalt sulfide nanoparticles decorated nitrogen and sulfur co-doped graphene nanosheets as an effective bifunctional oxygen catalyst. Its oxygen evolution reaction (OER) catalytic activity outperforms Pt/C, giving a current density of 38.19 mA cm−2 at 1.0 V. Zn–air batteries using this material on air-cathode show high stability and good rechargeability.

A water-soluble, supramolecular catalytic system has been designed based on inclusion complexation between a hydrophobic palladium(II)–dipyrazole complex bearing an adamantyl (Ad) molecular recognition moiety and a complementary, hydrophilic β-cyclodextrin (β-CD) derivative. The single-crystal molecular structure of the Pd(II) complex was determined and its host–guest inclusion complexation with heptakis(2,6-di-O-methyl)-β-CD (dmβ-CD) in an aqueous medium was confirmed by 2D NOESY 1H NMR spectroscopy. The catalyst showed high activity for Suzuki–Miyaura coupling of hydrophilic aryl bromides with aryl boronic acids in aqueous organic solvents. In the presence of n-Bu4NBr as a stabilizer, the catalyst-containing reaction solution can be recycled and reused multiple times to catalyze the coupling reaction of fresh substrates once the product has been removed by centrifugation. This work demonstrates a supramolecular complex approach, non-covalently modifying a water insoluble metal complex to provide a water-soluble inclusion system to serve as a recyclable catalyst for potential application in green chemical synthesis.

Three stair-step [Cu4I4] cluster-based complexes [Cu4I4(L1)2] (1), [Cu4I4(L2)]n (2) and [Cu4I4(L3)]n·2n(CH3CN) (3) and two linear Zn(II) coordination polymers [ZnCl2(L1)]n (4) and [ZnCl2(L3)]n (5) with 2-pyridyl-triazole ligands (L1 = 2-((4-propyl-1H-1,2,3-triazol-1-yl)methyl)pyridine, L2 = 1,3-bis(1-(pyridin-2-ylmethyl)-1H-1,2,3-triazol-4-yl)propane and L3 = 1,4-bis(1-(pyridin-2-ylmethyl)-1H-1,2,3-triazol-4-yl)butane) have been synthesized and characterized by single-crystal X-ray diffraction (XRD), powder XRD, thermogravimetric analysis and photoluminescence spectroscopy. Complex 1 possesses a stair-step [Cu4I4] cluster structure. Complexes 2 and 3 are 1-D polymeric forms of [Cu4I4] clusters. Complexes 4 and 5 are 1-D Zn(II) polymeric structures bridged by L1 and L3 spacers, respectively. In 1–3, ligands L1–L3 adopt a bidentate/monodentate dual coordination mode through the assistance of the triazole and pyridyl nitrogen donors. Ligand L1 exhibits an unusual open-bridging mode in complex 4, employing Npy and 3′-Ntri donors. By comparison, ligand L3 bridges two metal centers in complex 5 using 3,3′-Ntri donors. The structural (4-pyridyl- and 2-pyridyl-triazole) and H-bonding interaction effects on the coordination structures are described and discussed. All five complexes exhibit solid-state photoluminescence with maximum emission in the region of 440–490 nm.

Three new 1,2,3-triazole-based NS ligands, 2-((4-((benzylthio)methyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine (L1), 2-((4-(2-(cyclopentylthio)ethyl)-1H-1,2,3-triazol-1-yl)methyl)pyridine (L2) and 2-((4-(2-(cyclopentylthio)ethyl)-1H-1,2,3-triazol-1-yl)methyl)quinoline (L3) and the corresponding copper(I)-iodide complexes [Cu4I4(L1)2] (1), [Cu6I6(L2)2] (2) and [Cu6I6(L3)2] (3A) have been prepared and characterized by single-crystal X-ray diffraction (XRD), powder XRD, photoluminescence spectroscopy and thermogravimetric analysis. Complexes 1, 2 and 3A exhibit stair-step [CunIn] (n = 4 and 6) cluster structures with supporting ligands L1, L2 and L3, respectively. Ligand L1 coordinates with a bidentate/monodentate binding mode in the [Cu4I4] cluster complex 1 using the pyridyl–triazole moiety and with a pendant –CH2SCH2Ph group. Increasing the length of the bridge from –CH2– in L1 to –C2H4– in L2 and L3 engages the S donor and these ligands coordinate using a bidentate/monodentate/monodentate mode supporting larger [Cu6I6] cluster complexes 2 and 3A. A kinetic product [Cu8I8(L3)2(CH3CN)2] (3B) was isolated from the reaction of L3 with CuI in CH3CN and the single-crystal X-ray structure indicates a rare discrete stair-step [Cu8I8] core supported by two L3 and two coordinated CH3CN solvates. The structure is further stabilized by intermolecular π⋯π stacking interactions in the lattice. Isolation of 1–3 provides a good demonstration of the use of multidentate and multifunctional hybrid ligands in supporting [CunIn] clusters of different sizes (n = 4, 6, 8). Ligands L1–L3 are blue emissive molecules. The corresponding complexes display strong blue (1 and 2) or remarkable yellow (3A) emissions between 500 and 700 nm in the solid state. The structures of sulfur-containing ligands and their copper-iodide complexes are described and discussed.

A series of trapezoidal metallacycles were synthesized by the selective combination of a rigid with a flexible arm. [2]Catenane 3 was obtained by self-assembly when the cavity size of the trapezoidal rings was optimised.

In this paper, we discuss some key parameters in design of lithium sulfur batteries with high energy density, in particular carbon/sulfur ratio, sulfur loading density, electrolyte volume and electrode deformability, which directly impact the battery performance in terms of capacity, cycleability, and processibilities, etc. We find that a carbon to sulfur ratio of 1:2 (w/w) in the electrode is good for high specific capacity, giving a capacity of 538 mA h g −1 which is 3 times as high as that of LiCoO 2 cathode. The issue of fragileness for electrode at high sulfur loading density is mitigated by replacing carbon black with fine graphite powders. With these optimizations the carbon–sulfur electrode gives an energy density of 5.88 mW h cm −2 which corresponds to 60% of that of the commercial LiCoO 2 electrode.

The emergence of supramolecular chemistry has led to the discovery of a rising number of macrocycles and cages with a range of functionalities. Most of these supramolecular aggregates are metal coordination networks, whereas pure organic assemblies are less developed. Organic macrocycles and cages have the advantages of chemical robustness, processability in organic solvents, and suitability for pilot-scale applications. They are constructed primarily from covalent bonds, with irreversible and reversible bond types. We herein highlight the use of different versatile bonding approaches in engineering these soft materials, as well as their emerging applications, such as gas storage, thin films, liquid crystals, and catalysis.