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Vat photopolymerization 3D printing has proven very successful for the rapid additive manufacturing (AM) of polymeric parts at high resolution. However, the range of materials that can be printed and their resulting properties remains narrow. Herein, we report the successful AM of a series of poly(carbonate-b-ester-b-carbonate) elastomers, derived from carbon dioxide and bio-derived ϵ-decalactone. By employing a highly active and selective Co(II)Mg(II) polymerization catalyst, an ABA triblock copolymer (M n =6.3 kg mol -1 , Ð M =1.26) was synthesized, formulated into resins which were 3D printed using digital light processing (DLP) and a thiol-ene-based crosslinking system. A series of elastomeric and degradable thermosets were produced, with varying thiol cross-linker length and poly(ethylene glycol) content, to produce complex triply periodic geometries at high resolution. Thermomechanical characterization of the materials reveals printing-induced microphase separation and tunable hydrophilicity. These findings highlight how utilizing DLP can produce sustainable materials from low molar mass polyols quickly and at high resolution. The 3D printing of these functional materials may help to expedite the production of sustainable plastics and elastomers with potential to replace conventional petrochemical-based options., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Improving composite cathode function is key to the success of the solid-state battery. Maximizing attainable cathode capacity and retention requires integrating suitable polymeric binders that retain a sufficiently high ionic conductivity and long-term chemo-mechanical stability of the cathode active material-solid-electrolyte-carbon mixture. Herein, we report block copolymer networks composed of lithium borate polycarbonates and poly(ethylene oxide) that improved the capacity (200 mAh g -1 at 1.75 mA cm -2 ) and capacity retention (94 % over 300 cycles) of all-solid-state composite cathodes with nickel-rich LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode active material, Li 6 PS 5 Cl solid electrolyte, and carbon. Tetrahedral B(OR) 2 (OH) 2 - anions immobilized on the polycarbonate segments provide hydrogen-bonding chain crosslinking and selective Li-counterion conductivity, parameterized by Li-ion transference numbers close to unity (t Li+ ~0.94). With 90 wt % polycarbonate content and a flexible low glass transition temperature backbone, the single-ion conductors achieved high Li-ion conductivities of 0.2 mS cm -1 at 30 °C. The work should inform future binder design for improving the processability of cathode composites towards commercializing solid-state batteries, and allow use in other cell configurations, such as lithium-sulphur cathode designs., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Carbon dioxide copolymerization is a front-runner CO 2 utilization strategy but its viability depends on improving the catalysis. So far, catalyst structure-performance correlations have not been straightforward, limiting the ability to predict how to improve both catalytic activity and selectivity. Here, a simple measure of a catalyst ground-state parameter, metal reduction potential, directly correlates with both polymerization activity and selectivity. It is applied to compare performances of 6 new heterodinuclear Co(III)K(I) catalysts for propene oxide (PO)/CO 2 ring opening copolymerization (ROCOP) producing poly(propene carbonate) (PPC). The best catalyst shows an excellent turnover frequency of 389 h -1 and high PPC selectivity of >99 % (50 °C, 20 bar, 0.025 mol% catalyst). As demonstration of its utility, neither DFT calculations nor ligand Hammett parameter analyses are viable predictors. It is proposed that the cobalt redox potential informs upon the active site electron density with a more electron rich cobalt centre showing better performances. The method may be widely applicable and is recommended to guide future catalyst discovery for other (co)polymerizations and carbon dioxide utilizations., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Utilizing carbon dioxide (CO 2 ) to make polycarbonates through the ring-opening copolymerization (ROCOP) of CO 2 and epoxides valorizes and recycles CO 2 and reduces pollution in polymer manufacturing. Recent developments in catalysis provide access to polycarbonates with well-defined structures and allow for copolymerization with biomass-derived monomers; however, the resulting material properties are underinvestigated. Here, new types of CO 2 -derived thermoplastic elastomers (TPEs) are described together with a generally applicable method to augment tensile mechanical strength and Young's modulus without requiring material re-design. These TPEs combine high glass transition temperature (T g ) amorphous blocks comprising CO 2 -derived poly(carbonates) (A-block), with low T g poly(ε-decalactone), from castor oil, (B-block) in ABA structures. The poly(carbonate) blocks are selectively functionalized with metal-carboxylates where the metals are Na(I), Mg(II), Ca(II), Zn(II) and Al(III). The colorless polymers, featuring <1 wt% metal, show tunable thermal (T g ), and mechanical (elongation at break, elasticity, creep-resistance) properties. The best elastomers show >50-fold higher Young's modulus and 21-times greater tensile strength, without compromise to elastic recovery, compared with the starting block polymers. They have wide operating temperatures (-20 to 200 °C), high creep-resistance and yet remain recyclable. In the future, these materials may substitute high-volume petrochemical elastomers and be utilized in high-growth fields like medicine, robotics, and electronics., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo-copper precursor, mesitylcopper(I) [CuMes] z (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu 2 O or Cu 2 S nanoparticles. Use of sub-stoichiometric quantities of protonated ligand (pro-ligand; 0.1-0.2 equivalents vs. [CuMes] z ) allows saturation of surface coordination sites but avoids excess pro-ligand contaminating the nanoparticle solutions. The pro-ligands are nonanoic acid (HO 2 CR 1 ), 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (HO 2 CR 2 ) or di(thio)nonanoic acid, (HS 2 CR 1 ), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu 2 O is preferentially coordinated by carboxylate ligands and Cu 2 S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well-defined nanoparticles and the need for appropriate ligand selection., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A series of dynamic metalloporphyrin [2]rotaxane molecular shuttles comprising of bis-functionalised Zn(II) porphyrin axle and pyridyl functionalised macrocycle components are prepared in high yield via active metal template synthetic methodology. Extensive variable temperature 1 H NMR and quantitative UV-Vis spectroscopic titration studies demonstrate dynamic macrocycle translocation is governed by an inter-component co-ordination interaction between the macrocycle pyridyl and axle Zn(II) metalloporphyrin, which serves to bias a 'resting state' co-conformation. The dynamic shuttling behaviour of the interlocked structures is dramatically inhibited by the addition of a neutral Lewis base such as pyridine, but can also be tuned via post-synthetic rotaxane demetallation of the porphyrin axle core to give free-base, or upon subsequent metallation, Ni(II) [2]rotaxane analogues. Importantly, the Lewis acidic Zn(II) porphyrin axle component is also capable of coordinating anions which induces mechanical bond shuttling behaviour resulting in a novel optical sensing response., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Thermoplastic elastomers based on polyesters/carbonates have the potential to maximize recyclability, degradability and renewable resource use. However, they often underperform and suffer from the familiar trade-off between strength and extensibility. Herein, we report well-defined reprocessable poly(ester-b-carbonate-b-ester) elastomers with impressive tensile strengths (60 MPa), elasticity (>800 %) and recovery (95 %). Plus, the ester/carbonate linkages are fully degradable and enable chemical recycling. The superior performances are attributed to three features: (1) Highly entangled soft segments; (2) Fully reversible strain-induced crystallization and (3) Precisely placed Zn II -carboxylates dynamically crosslinking the hard domains. The one-pot synthesis couples controlled cyclic monomer ring-opening polymerization and alternating epoxide/anhydride ring-opening copolymerization. Efficient convresion to ionomers is achieved by reacting vinyl-epoxides to install Zn II -carboxylates., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Electrocatalytic hydrogen gas production is considered a potential pathway towards carbon-neutral energy sources. However, the development of this technology is hindered by the lack of efficient, cost-effective, and environmentally benign catalysts. In this study, a main-group-element-based electrocatalyst, SbSalen, is reported to catalyze the hydrogen evolution reaction (HER) in an aqueous medium. The heterogenized molecular system achieved a Faradaic efficiency of 100 % at -1.4 V vs. NHE with a maximum current density of -30.7 mA/cm 2 . X-ray photoelectron spectroscopy of the catalyst-bound working electrode before and after electrolysis confirmed the molecular stability during catalysis. The turnover frequency was calculated as 43.4 s -1 using redox-peak integration. The kinetic and mechanistic aspects of the electrocatalytic reaction were further examined by computational methods. This study provides mechanistic insights into main-group-element electrocatalysts for heterogeneous small-molecule conversion., (© 2022 Wiley-VCH GmbH.)

Chemical recycling of polymers to true monomers is pivotal for a circular plastics economy. Here, the first catalyzed chemical recycling of the widely investigated carbon dioxide derived polymer, poly(cyclohexene carbonate), to cyclohexene oxide and carbon dioxide is reported. The reaction requires dinuclear catalysis, with the di-Mg II catalyst showing both high monomer selectivity (>98 %) and activity (TOF=150 h -1 , 0.33 mol %, 120 °C). The depolymerization occurs via a chain-end catalyzed depolymerization mechanism and DFT calculations indicate the high selectivity arises from Mg-alkoxide catalyzed epoxide extrusion being kinetically favorable compared to cyclic carbonate formation., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The catalysed ring opening copolymerizations (ROCOP) of carbon dioxide/epoxide or anhydride/epoxide are controlled polymerizations that access useful polycarbonates and polyesters. Here, a systematic investigation of a series of heterodinuclear Mg(II)M(II) complexes reveals which metal combinations are most effective. The complexes combine different first row transition metals (M(II)) from Cr(II) to Zn(II), with Mg(II); all complexes are coordinated by the same macrocyclic ancillary ligand and by two acetate co-ligands. The complex syntheses and characterization data, as well as the polymerization data, for both carbon dioxide/cyclohexene oxide (CHO) and endo-norbornene anhydride (NA)/cyclohexene oxide, are reported. The fastest catalyst for both polymerizations is Mg(II)Co(II) which shows propagation rate constants (k p ) of 34.7 mM -1  s -1 (CO 2 ) and 75.3 mM -1  s -1 (NA) (100 °C). The Mg(II)Fe(II) catalyst also shows excellent performances with equivalent rates for CO 2 /CHO ROCOP (k p =34.7 mM -1  s -1 ) and may be preferable in terms of metallic abundance, low cost and low toxicity. Polymerization kinetics analyses reveal that the two lead catalysts show overall second order rate laws, with zeroth order dependencies in CO 2 or anhydride concentrations and first order dependencies in both catalyst and epoxide concentrations. Compared to the homodinuclear Mg(II)Mg(II) complex, nearly all the transition metal heterodinuclear complexes show synergic rate enhancements whilst maintaining high selectivity and polymerization control. These findings are relevant to the future design and optimization of copolymerization catalysts and should stimulate broader investigations of synergic heterodinuclear main group/transition metal catalysts., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Heteroatom-containing polymers have strong potential as sustainable replacements for petrochemicals, show controllable monomer-polymer equilibria and properties spanning plastics, elastomers, fibres, resins, foams, coatings, adhesives, and self-assembled nanostructures. Their current and future applications span packaging, house-hold goods, clothing, automotive components, electronics, optical materials, sensors, and medical products. An interesting route to these polymers is the catalysed ring-opening copolymerisation (ROCOP) of heterocycles and heteroallenes. It is a living polymerization, occurs with high atom economy, and creates precise, new polymer structures inaccessible by traditional methods. In the last decade there has been a renaissance in research and increasing examples of commercial products made using ROCOP. It is better known in the production of polycarbonates and polyesters, but is also a powerful route to make N-, S-, and other heteroatom-containing polymers, including polyamides, polycarbamates, and polythioesters. This Review presents an overview of the different catalysts, monomer combinations, and polymer classes that can be accessed by heterocycle/heteroallene ROCOP., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A series heterodinuclear catalysts, operating without co-catalyst, show good performances for the ring opening copolymerization (ROCOP) of cyclohexene oxide and carbon dioxide. The complexes feature a macrocyclic ligand designed to coordinate metals such as Zn(II), Mg(II) or Co(III), in a Schiff base 'pocket', and Na(I) in a modified crown-ether binding 'pocket'. The 11 new catalysts are used to explore the influences of the metal combinations and ligand backbones over catalytic activity and selectivity. The highest performance catalyst features the Co(III)Na(I) combination, [N,N'-bis(3,3'-triethylene glycol salicylidene)-1,2-ethylenediamino cobalt(III) di(acetate)]sodium (7), and it shows both excellent activity and selectivity at 1 bar carbon dioxide pressure (TOF=1590 h -1 , >99 % polymer selectivity, 1 : 10: 4000, 100 °C), as well as high activity at higher carbon dioxide pressure (TOF=4343 h -1 , 20 bar, 1 : 10 : 25000). Its rate law shows a first order dependence on both catalyst and cyclohexene oxide concentrations and a zeroth order for carbon dioxide pressure, over the range 10-40 bar. These new catalysts eliminate any need for ionic or Lewis base co-catalyst and instead exploit the coordination of earth-abundant and inexpensive Na(I) adjacent to a second metal to deliver efficient catalysis. They highlight the potential for well-designed ancillary ligands and inexpensive Group 1 metals to deliver high performance heterodinuclear catalysts for carbon dioxide copolymerizations and, in future, these catalysts may also show promise in other alternating copolymerization and carbon dioxide utilizations., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A challenge in polymer synthesis using CO 2 is to precisely control CO 2 placement in the backbone and chain end groups. Here, a new catalyst class delivers unusual selectivity and is self-switched between different polymerization cycles to construct specific sequences and desirable chain-end chemistries. The best catalyst is a trinuclear dizinc(II)sodium(I) complex and it functions without additives or co-catalysts. It shows excellent rates across different ring-opening (co)polymerization catalytic cycles and allows precise control of CO 2 incorporation within polyesters and polyethers, thereby allowing access to new polymer chemistries without requiring esoteric monomers, multi-reactor processes or complex post-polymerization procedures. The structures, kinetics and mechanisms of the catalysts are investigated, providing evidence for intermediate speciation and uncovering the factors governing structure and composition and thereby guiding future catalyst design., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In this work, the electrocatalytic reduction of dichloromethane (CH 2 Cl 2 ) into hydrocarbons involving a main group element-based molecular triazole-porphyrin electrocatalyst H2PorT8 is reported. This catalyst converted CH 2 Cl 2 in acetonitrile to various hydrocarbons (methane, ethane, and ethylene) with a Faradaic efficiency of 70 % and current density of -13 mA cm -2 at a potential of -2.2 V vs. Fc/Fc + using water as a proton source. The findings of this study and its mechanistic interpretations demonstrated that H2PorT8 was an efficient and stable catalyst for the hydrodechlorination of CH 2 Cl 2 and that main group catalysts could be potentially used for exploring new catalytic reaction mechanisms., (© 2021 Wiley-VCH GmbH.)

A new class of bio-based fully degradable block polyesters are pressure-sensitive adhesives. Bio-derived monomers are efficiently polymerized to make block polyesters with controlled compositions. They show moderate to high peel adhesions (4-13 N cm -1 ) and controllable storage and loss moduli, and they are removed by adhesive failure. Their properties compare favorably with commercial adhesives or bio-based polyester formulations but without the need for tackifier or additives., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

The control of the second coordination sphere in a coordination complex plays an important role in improving catalytic efficiency. Herein, we report a zinc porphyrin complex ZnPor8T with multiple flexible triazole units comprising the second coordination sphere, as an electrocatalyst for the highly selective electrochemical reduction of carbon dioxide (CO 2 ) to carbon monoxide (CO). This electrocatalyst converted CO 2 to CO with a Faradaic efficiency of 99 % and a current density of -6.2 mA cm -2 at -2.4 V vs. Fc/Fc + in N,N-dimethylformamide using water as the proton source. Structure-function relationship studies were carried out on ZnPor8T analogs containing different numbers of triazole units and distinct triazole geometries; these unveiled that the triazole units function cooperatively to stabilize the CO 2 -catalyst adduct in order to facilitate intramolecular proton transfer. Our findings demonstrate that incorporating triazole units that function in a cooperative manner is a versatile strategy to enhance the activity of electrocatalytic CO 2 conversion., (© 2020 Wiley-VCH GmbH.)

Redox-flow batteries (RFBs) are a highly promising large-scale energy storage technology for mitigating the intermittent nature of renewable energy sources. Here, the design and implementation of a micellization strategy in an anthraquinone-based, pH-neutral, nontoxic, and metal-free aqueous RFB is reported. The micellization strategy (1) improves stability by protecting the redox-active anthraquinone core with a hydrophilic poly(ethylene glycol) shell and (2) increases the overall size to mitigate the crossover issue through a physical blocking mechanism. Paired with a well-established potassium ferrocyanide catholyte, the micelle-based RFB displayed an excellent capacity retention of 90.7 % after 3600 charge/discharge cycles (28.3 days), corresponding to a capacity retention of 99.67 % per day and 99.998 % per cycle. The mechanistic studies of redox-active materials were also conducted and indicated the absence of side reactions commonly observed in other anthraquinone-based RFBs. The outstanding performance of the RFB demonstrates the effectiveness of the micellization strategy for enhancing the performance of organic material-based aqueous RFBs., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The effects of primary and second coordination spheres on molecular electrocatalysis have been extensively studied, yet investigations of third functional spheres are rarely reported. Here, an electrocatalyst (ZnPEG8T) was developed with a hydrophilic channel as a third functional sphere that facilitates relay proton shuttling to the primary and second coordination spheres for enhanced catalytic CO 2 reduction. Using foot-of-the-wave analysis, the ZnPEG8T catalyst displayed CO 2 -to-CO activity (TOF max ) thirty times greater than that of the benchmark catalyst without a third functional sphere. A kinetic isotopic effect (KIE) study, in conjunction with voltammetry and UV/Vis spectroscopy, uncovered that the rate-limiting step was not the protonation step of the metallocarboxylate intermediate, as observed in many other molecular CO 2 reduction electrocatalysts, but rather the replenishment of protons in the proton-shuttling channel. Controlled-potential electrolysis using ZnPEG8T displayed a faradaic efficiency of 100 % for CO 2 -to-CO conversion at -2.4 V vs. Fc/Fc + . A Tafel plot was also generated for a comparison to other reported molecular catalysts. This report validates a strategy for incorporating higher functional spheres for enhanced catalytic efficiency in proton-coupled electron-transfer reactions., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polylactide (PLA) is a fully biodegradable and recyclable plastic, produced from a bio-derived monomer: it is a circular economy plastic. Its properties depend upon its stereochemistry and isotactic PLA shows superior thermal-mechanical performances. Here, a new means to control tacticity by exploiting rotaxane conformational dynamism is described. Dynamic achiral [2]rotaxanes can show high isoselectivity (P i =0.8, 298 K) without requiring any chiral additives and enchain by a chain end control mechanism. The organocatalytic dynamic stereoselectivity is likely applicable to other small-molecule and polymerization catalyses., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis and aqueous self-assembly of a new class of amphiphilic aliphatic polyesters are presented. These AB block polyesters comprise polycaprolactone (hydrophobe) and an alternating polyester from succinic acid and an ether-substituted epoxide (hydrophile). They self-assemble into biodegradable polymersomes capable of entering cells. Their degradation products are bioactive, giving rise to differentiated cellular responses inducing stromal cell proliferation and macrophage apoptosis. Both effects emerge only when the copolymers enter cells as polymersomes and their magnitudes are size dependent., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Switchable polymerisation catalysis enables block polymer sequence selectivity from monomer mixtures, resulting in the formation of multiblock polyesters. The aluminium salphen catalyst switches between two different polymerisation mechanisms and selectively enchains mixtures of commercially available monomers: lactide, phthalic anhydride, and propene oxide. Sequential monomer mixture additions yield multi-block polyesters featuring 3, 7, 11, 15, 19, 23, and 27 blocks. The unparalleled catalytic selectivity can be used to access completely new multi-block polyesters relevant for future applications., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

ABA triblock polyesters are synthesized using a commercially available chromium salen catalyst, in one pot, from monomer mixtures comprising epoxide, anhydride and lactone. The catalysis is highly selective and applies a single catalyst in two distinct pathways. It occurs first by epoxide/anhydride ring-opening copolymerization and subsequently by lactone ring-opening polymerization. It is used to produce various new ABA polyester polyols; these polyols can undergo post-functionalization and chain-extension reactions. The ability to use a commercial catalyst and switchable catalysis with monomer mixtures is expected to facilitate future explorations of new classes of block polymers., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two new di-zinc-aryl complexes, [LZn 2 Ph 2 ] and [LZn 2 (C 6 F 5 ) 2 ], coordinated by a diphenol tetraamine macrocyclic ligand have been prepared and fully characterised, including by single-crystal X-ray diffraction experiments. The complexes' reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, isopropanol and phenol were investigated using both experimental studies and density functional theory calculations. In particular, [LZn 2 Ph 2 ] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn 2 (C 6 F 5 ) 2 ] does not react. Under these conditions [LZn 2 Ph 2 ] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide/carbon dioxide (TOF=20 h -1 ), cyclohexene oxide/phthalic anhydride (TOF=33 h -1 ) and the ring-opening polymerisations of rac-lactide (TOF=99 h -1 ) and ϵ-caprolactone (TOF=5280 h -1 )., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Polylactide (PLA) is the leading bioderived polymer produced commercially by the metal-catalyzed ring-opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac-lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m -1  min -1 , THF, 298 K), high control, low loadings (0.2 mol %), and isoselectivity (P i =0.92, THF, 258 K). Furthermore, the phosphasalen indium catalysts do not require any chiral additives., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Developing selective polymerizations from complex monomer mixtures is an important challenge. Here, dinuclear catalysts allow selective polymerization from mixtures of sterically hindered tricyclic anhydrides, carbon dioxide and epoxides to yield well-controlled copoly(ester-carbonates). Surprisingly, two very similar homogeneous catalysts differing only in the central metal, zinc versus magnesium, show very high but diametrically opposite monomer selectivity. The selectivity is attributed to different polymerization kinetics and to steric factors associated with the anhydrides., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Understanding how to moderate and improve catalytic activity is critical to improving degradable polymer production. Here, di- and monozinc catalysts, coordinated by bis(imino)diphenylamido ligands, show remarkable activities and allow determination of the factors controlling performance. In most cases, the dizinc catalysts significantly out-perform the monozinc analogs. Further, for the best dizinc catalyst, the ligand conformation controls activity: the catalyst with "folded" ligand conformation shows turnover frequency (TOF) values up to 60 000 h(-1) (0.1 mol % loading, 298 K, [LA]=1 m), whilst that with a "planar" conformation is much slower, under similar conditions (TOF=30 h(-1) ). Dizinc catalysts also perform very well under immortal conditions, showing improved control, and are able to tolerate loadings as low as 0.002 mol % whilst conserving high activity (TOF=12 500 h(-1) )., (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Bacterial cellulose (BC) is often regarded as a prime candidate nano-reinforcement for the production of renewable nanocomposites. However, the mechanical performance of most BC nanocomposites is often inferior compared with commercially available polylactide (PLLA). Here, the manufacturing concept of paper-based laminates is used, i.e., "PaPreg," to produce BC nanopaper reinforced PLLA, which has been called "nanoPaPreg" by the authors. It is demon-strated that high-performance nanoPaPreg (vf = 65 vol%) with a tensile modulus and strength of 6.9 ± 0.5 GPa and 125 ± 10 MPa, respectively, can be fabricated. It is also shown that the tensile properties of nanoPaPreg are predominantly governed by the mechanical performance of BC nanopaper instead of the individual BC nanofibers, due to difficulties impregnating the dense nanofibrous BC network., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Iso-selective initiators for the ring-opening polymerization (ROP) of rac-lactide are rare outside of Group 13. We describe the first examples of highly iso-selective lutetium initiators. The phosphasalen lutetium ethoxide complex shows excellent iso-selectivity, with a P(i) value of 0.81-0.84 at 298 K, excellent rates, and high degrees of polymerization control. Conversely, the corresponding La derivative exhibits moderate heteroselectivity (P(s)=0.74, 298 K). Thus, the choice of metal center is shown to be crucial in determining the level and mode of stereocontrol. The relative order of rates for the series of complexes is inversely related to metallic covalent radius: that is, La>Y>Lu., (© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.)

A novel chemoselective polymerization control yields predictable (co)polymer compositions from a mixture of monomers. Using a dizinc catalyst and a mixture of caprolactone, cyclohexene oxide, and carbon dioxide enables the selective preparation of either polyesters or polycarbonates or copoly(ester-carbonates). The selectivity depends on the nature of the zinc-oxygen functionality at the growing polymer chain end, and can be controlled by the addition of exogeneous switch reagents., (Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metal alkynyl complexes hold a fascination for synthetic chemists, structural chemists, and materials scientists alike. Harnessing the unique overlap of metal and carbon orbitals is a challenge that can be overcome in many ways and hence, there are many synthetic routes toward M-C=C-bond-forming reactions that utilize a wide variety of transition-metal and alkynyl reagents. Some methods can be widely applied, while others are specific to a particular metal or compound. The linear geometry of the alkynyl unit and its pi-unsaturated character have led to metal alkynyls becoming attractive building blocks for molecular wires and polymeric organometallic materials, which can possess interesting properties, such as optical nonlinearity, luminescence, liquid crystallinity, and electrical conductivity. A unique, multifaceted approach, often combining talents from all three of the above chemical disciplines, has served as a driving force behind the intense research into the development of metal alkynyl sigma complexes, the progress of which, particularly in the last ten years, is summarized in this review.