Search

Closed-loop recycling offers the opportunity to mitigate plastic waste through reversible polymer construction and deconstruction. Although examples of chemical recycling of polymers are known, few have been applied to materials derived from abundant commodity olefinic monomers, which are the building blocks of ubiquitous plastic resins. Here we describe a [2+2] cycloaddition/oligomerization of 1,3-butadiene to yield a previously unrealized telechelic microstructure of (1,n′-divinyl)oligocyclobutane. This material is thermally stable, has stereoregular segments arising from chain-end control, and exhibits high crystallinity even at low molecular weight. Exposure of the oligocyclobutane to vacuum in the presence of the pyridine(diimine) iron precatalyst used to synthesize it resulted in deoligomerization to generate pristine butadiene, demonstrating a rare example of closed-loop chemical recycling of an oligomeric material derived from a commodity hydrocarbon feedstock. Iron-catalysed [2+2] cycloaddition/oligomerization of neat butadiene affords (1,n′-divinyl)oligocyclobutane—a telechelic, crystalline material consisting of 1,3-enchained cyclobutyl units. This oligocyclobutane can be chemically recycled to pure butadiene using the same iron catalyst employed in its synthesis, demonstrating design principles for next-generation plastic materials that can be returned to pristine monomer.

Aryl-substituted pyridine(diimine) iron complexes promote the catalytic [2+2] cycloadditions of alkenes and dienes to form vinylcyclobutanes as well as the oligomerization of butadiene to generate divinyl(oligocyclobutane), a microstructure of poly(butadiene) that is chemically recyclable. A systematic study on a series of iron butadiene complexes as well as their ruthenium congeners has provided insights into the essential features of the catalyst that promotes these cycloaddition reactions. Structural and computational studies on iron butadiene complexes identified that the structural rigidity of the tridentate pincer enables rare s-trans diene coordination. This geometry, in turn, promotes dissociation of one of the alkene arms of the diene, opening a coordination site for the incoming substrate to engage in oxidative cyclization. Studies on ruthenium congeners has established that this step occurs without redox involvement of the pyridine(diimine) chelate. Cyclobutane formation occurs from a metallacyclic intermediate by reversible C(sp(3))–C(sp(3)) reductive coupling. A series of labeling experiments with pyridine(diimine) iron and ruthenium complexes support the favorability of accessing the +3 oxidation state to trigger C(sp(3))–C(sp(3)) reductive elimination, involving spin crossover from S = 0 to S = 1. The high density of states of iron and the redox-active pyridine(diimine) ligand facilitate this reactivity under thermal conditions. For the ruthenium congener, the pyridine(diimine) remains redox innocent and irradiation with blue light was required to promote the analogous reactivity. These structure-activity relationships highlight important design principles for the development of next generation catalysts for these cycloaddition reactions as well as to promote chemical recycling of cycloaddition polymers.

Diene self-exchange reactions of the 17-electron, formally cobalt(0) cyclooctadienyl precatalyst, (R,R)-(iPrDuPhos)Co(COD) (P2CoCOD, (R,R)-iPrDuPhos = 1,2-bis((2R,5R)-2,5-diisopropylphospholano)benzene, COD = 1,5-cyclooctadiene) were studied using natural abundance and deuterated 1,5-cyclooctadiene. Exchange of free and coordinated diene was observed at ambient temperature in benzene-d6 solution and kinetic studies support a dissociative process. Both neutral P2CoCOD and the 16-electron, cationic cobalt(I) complex, [(R,R)-(iPrDuPhos)Co(COD)][BArF4] (BArF4 = B[(3,5-(CF3)2)C6H3]4) underwent instantaneous displacement of the 1,5-cyclooctadiene ligand by carbon monoxide and generated the corresponding carbonyl derivatives. The solid-state parameters, DFT-computed Mulliken spin density and analysis of molecular orbitals suggest an alternative description of P2CoCOD as low-spin cobalt(II) with the 1,5-cyclooctadiene acting as a LX2-type ligand. This view of the electronic structure provides insight into the nature of the ligand substitution process and the remarkable stability of the neutral cobalt complexes toward protic solvents observed during catalytic alkene hydrogenation.

Aryl carbonates, a common protecting group in synthetic organic chemistry, are potentially valuable electrophiles in cross-coupling reactions. Here, after performing a thorough evaluation of different precatalysts, we demonstrate that (dcypf)Ni(2-ethylphenyl)(Br) (dcypf = 1,1-bis-(dicyclohexylphosphino)ferrocene) is an efficient precatalyst for Suzuki-Miyaura reactions using a variety of aryl carbonates as substrates. Mechanistic studies indicate that (dcypf)Ni(2-ethylphenyl)(Br), which contains a bidentate phosphine that binds in a trans geometry, is an effective precatalyst for these reactions for two reasons: (i) it rapidly forms the Ni(O) active species and (ii) it minimizes comproportionation reactions between the Ni(O) active species and both the unactivated Ni(II) precatalyst and on-cycle Ni(II) complexes to form catalytically inactive Ni(I) species. In contrast, the state of the art precatalyst (dppf)Ni(o-tolyl)(Cl) (dppf = 1,1-bis(diphenylphosphino)ferrocene), which contains a bidentate phosphine that binds in a cis geometry, forms Ni(I) species during activation and is essentially inactive for aryl carbonate couplings. Although the exact reasons on a molecular level why the dcypf system is more active than the dppf system are unclear, our results indicate that in general Ni catalysts supported by the dcypf ligand will give better performance for catalytic reactions involving substrates which undergo relatively slow oxidative addition, such as aryl carbonates.

A number of new transition metal catalyzed methods for the formation of C(sp2 )-C(sp3 ) bonds have recently been described. These reactions often utilize bidentate polypyridyl-ligated Ni catalysts, and paramagnetic NiI halide or aryl species are proposed in the catalytic cycles. However, there is little knowledge about complexes of this type. Here, we report the synthesis of paramagnetic bidentate polypyridyl-ligated Ni halide and aryl complexes through elementary reactions proposed in catalytic cycles for C(sp2 )-C(sp3 ) bond formation. We investigate the ability of these complexes to undergo organometallic reactions that are relevant to C(sp2 )-C(sp3 ) coupling through stoichiometric studies and also explore their catalytic activity.

Closed-loop recycling offers the opportunity to help mitigate plastic waste through reversible polymer construction and deconstruction. While examples of the chemical recycling polymers are known, few have been applied to materials derived from abundant commodity olefinic monomers that are the building blocks of ubiquitous plastic resins. Here we describe a [2+2] cycloaddition oligomerization of 1,3-butadiene to yield a previously unrealized telechelic microstructure of (1,n’-divinyl)oligocyclobutane. This material is thermally stable, has stereoregular segments arising from chain-end control, and exhibits high crystallinity even at low molecular weight. Exposure of the oligocyclobutane to vacuum in the presence of the pyridine(diimine) iron precatalyst used to synthesize it resulted in deoligomerization to generate pristine butadiene, demonstrating a rare example of closed-loop chemical recycling of an oligomeric material derived from a commodity hydrocarbon feedstock.

Non-fullerene organic solar cells (OSCs) have attracted tremendous interest because of their potential to replace traditional expensive fullerene-based OSCs. To further increase the power conversion efficiency (PCE), it is necessary to offset the narrow absorption of the non-fullerene materials, which is often achieved by adding an additive (>10 wt%) to form a ternary blend. However, a high ratio of the third component can often be detrimental to the active layer morphology and can increase the complexity in understanding the device physics toward rationally designed improvements. In this work, we introduce 2,4-bis-[(N,N-diisobutylamino)-2,6-dihydroxyphenyl]-4-(4-diphenyliminio) squaraine (ASSQ) in the poly [(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl) benzo [1,2-b:4,5-b′] dithiophene)-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl) benzo [1,2-c:4,5-c′] dithiophene-4,8-dione)] (PBDB-T): 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno [2,3-d:2′,3′-d′]-s-indaceno [1,2-b:5,6-b′] dithiophene (ITIC) as an active layer “crystallizing-agent”. Through detailed morphology characterization, we find that the addition of 4 wt% ASSQ assists ITIC organization order and promotes PDBD-T:ITIC aggregation in the preferential face-on orientation. In addition, we demonstrate that the ASSQ and PBDB-T show efficient exciton dissociation in the ternary blend over Forster resonance energy transfer (FRET). We reveal using surface potential and solubility measurements that a ASSQ-ITIC co-crystalline structure forms which facilitates a significant improvement in the device PCE, from 8.98% to 10.86%.

Over the past decade, there has been significant improvement in the performance of polymer solar cells (PSCs). Devices with power conversion efficiency (PCE) well over 10% have been developed and in some cases the estimated device lifetime is approaching 10 years. In contrast, there has been limited research into the aesthetics of PSCs, which may be crucial to successful commercialization. Here, we report a variety of colored polymer solar cells by employing different amounts of an energy transfer dye molecule in a polymer-polymer binary photoactive system. In fact, by varying the amount of the dye molecule in the device, PSCs covering one third of the Munsell standard color chart (in this case green to red) are observed. Additionally, the dye molecule serves as an energy transfer donor to the host photoactive system which leads to 10% enhancement in PCE. Our approach may broaden the appeal of PSCs in applications where aesthetics are important.

Nickel precatalysts are potentially a more sustainable alternative to traditional palladium precatalysts for the Suzuki–Miyaura coupling reaction. Currently, there is significant interest in Suzuki–Miyaura coupling reactions involving readily accessible phenolic derivatives such as aryl sulfamates, as the sulfamate moiety can act as a directing group for the prefunctionalization of the aromatic backbone of the electrophile prior to cross-coupling. By evaluating complexes in the Ni(0), (I), and (II) oxidation states we report a precatalyst, (dppf)Ni(o-tolyl)(Cl) (dppf = 1,1′-bis(diphenylphosphino)-ferrocene), for Suzuki–Miyaura coupling reactions involving aryl sulfamates and boronic acids, which operates at a significantly lower catalyst loading and at milder reaction conditions than other reported systems. In some cases it can even function at room temperature. Mechanistic studies on precatalyst activation and the speciation of nickel during catalysis reveal that Ni(I) species are formed in the catalytic reaction via two different pathways: (i) the precatalyst (dppf)Ni(o-tolyl)(Cl) undergoes comproportionation with the active Ni(0) species; and (ii) the catalytic intermediate (dppf)Ni(Ar)(sulfamate) (Ar = aryl) undergoes comproportionation with the active Ni(0) species. In both cases the formation of Ni(I) is detrimental to catalysis, which is proposed to proceed via a Ni(0)/Ni(II) cycle. DFT calculations are used to support experimental observations and provide insight about the elementary steps involved in reactions directly on the catalytic cycle, as well as off-cycle processes. Our mechanistic investigation provides guidelines for designing even more active nickel catalysts.

Structural characterization of lignin extracted from the bio-oil produced by fast pyrolysis of switchgrass (Panicum virgatum) is reported. This is important for understanding the utility of lignin as a chemical feedstock in a pyrolysis-based biorefinery scheme. Pyrolysis induces a variety of structural changes to lignin in addition to reduction in molecular weight. The guaiacol structural units remain largely intact, and some hemicellulose stays covalently linked to the lignin. However, two-dimensional 1H–13C HSQC NMR analysis shows an absence of γ-methylene hydrogens from β-O-4 linkages, implying that rearrangements in the propyl linking chains have occurred. Ferulate and hydroxyl phenol esters are still present in the pyrolyzed lignin, but at lower concentrations than in unpyrolyzed switchgrass lignin.

There is currently significant interest in the development of efficient nickel precatalysts for cross-coupling. In this work, 14 nickel(II) precatalysts of the form (dppf)Ni(aryl)(X) (dppf = 1,1'-bis(diphenylphosphino)-ferrocene, X = Cl, Br) were synthesized. In particular, both the electronic and steric properties of the aryl group were modified to understand how this affects precatalyst activation. Using EPR spectroscopy, it was demonstrated that the amount of off-cycle nickel(I) species which are formed via comproportionation during precatalyst activation varies depending on the nature of the aryl group. For example, sterically bulky aryl groups reduce comproportionation. Additionally, the catalytic activity of the family of precatalysts was evaluated in five different Suzuki-Miyaura coupling reactions. The results from these catalytic studies provide information about how precatalyst structure affects catalytic efficiency, which may be useful for the rational design of improved nickel precatalysts for cross-coupling.

In this work, Ni(I) aryl species that are directly relevant to cross-coupling have been synthesized. Transmetalation of (dppf)Ni(I)X (dppf = 1,1′-bis(diphenylphosphino)-ferrocene, X = Cl, Br) with aryl Grignard reagents or aryl boronic acids in the presence of base produces Ni(I) aryl species of the form (dppf)Ni(I)(Ar) (Ar = Ph, o-tolyl, 2,6-xylyl, 2,4,6-mesityl, 2,4,6-(i)Pr(3)C(6)H(2)). The stability of the Ni(I) aryl species is inversely correlated to the steric bulk on the aryl ligand. The most unstable Ni(I) aryl species are the most active precatalysts for Suzuki–Miyaura reactions because they rapidly decompose to generate the active Ni(0) catalyst. This study shows that Ni(I) aryl species are initially formed in the activation of Ni(I) halide precatalysts for Suzuki–Miyaura reactions and establishes their stoichiometric and catalytic reactivity profile.

We demonstrate color tunable polymer solar cells by employing an energy transfer dye molecule in a polymerpolymer binary photoactive system. The guest dye molecule functions as energy transfer donor to the host photoactive system allowing the solar cell color to range from blue green to purple red without any significant efficiency decrease. In this proceeding we re-empathize the importance of the results and discussions which were published in Nano Energy in 2017 [1].

Esters are valuable electrophiles for cross-coupling due to their ubiquity and ease of synthesis. However, harsh conditions are traditionally required for the effective cross-coupling of ester substrates. Utilizing a recently discovered precatalyst, Pd-catalyzed Suzuki–Miyaura and Buchwald–Hartwig reactions involving cleavage of the C(acyl)–O bond of aryl esters that proceed under mild conditions are reported. The Pd(II) precatalyst is highly active because it is reduced to the Pd(0) active species more rapidly than previous precatalysts.

Ni-based precatalysts for the Suzuki-Miyaura reaction have potential chemical and economic advantages compared to commonly used Pd systems. Here, we compare Ni precatalysts for the Suzuki-Miyaura reaction supported by the dppf ligand in 3 oxidation states, 0, I and II. Surprisingly, at 80 °C they give similar catalytic activity, with all systems generating significant amounts of Ni(I) during the reaction. At room temperature a readily accessible bench-stable Ni(II) precatalyst is highly active and can couple synthetically important heterocyclic substrates. Our work conclusively establishes that Ni(I) species are relevant in reactions typically proposed to involve exclusively Ni(0) and Ni(II) complexes.

Transition metal-catalysed cross-coupling is one of the most powerful synthetic methods and has led to vast improvements in the synthesis of pharmaceuticals, agrochemicals and precursors for materials chemistry. A major advance in cross-coupling over the past 20 years is the utilization of well-defined, bench-stable Pd and Ni precatalysts that do not require the addition of free ancillary ligand, which can hinder catalysis by occupying open coordination sites on the metal. The development of precatalysts has resulted in new reactions and expanded substrate scopes, enabling transformations under milder conditions and with lower catalyst loadings. This Review highlights recent advances in the development of Pd and Ni precatalysts for cross-coupling, and provides a critical comparison between the state of the art in Pd- and Ni-based systems. Elaborate molecules can be assembled in a relatively mild manner through organic cross-coupling reactions, with those mediated by group 10 metal complexes being particularly useful. This Review covers the development of nickel and palladium precatalysts, comparing state-of-the-art systems and offering design principles for future technologies.

Using a recently discovered precatalyst, the first Pd-catalyzed Suzuki–Miyaura reactions using aryl sulfamates that occur at room temperature are reported. In complementary work, it is demonstrated that a related precatalyst can facilitate the coupling of aryl silanolates, which are less toxic and reactive nucleophiles than boronic acids with aryl chlorides. By combining our results using modern electrophiles and nucleophiles, the first Hiyama–Denmark reactions using aryl sulfamates are reported.

A series of PtII and PtIV aminotroponimate (ATI = N-tolyl-aminotroponiminate) complexes has been prepared. The PtII complex (ATI)Pt(CH3)(SMe2) (1a) is synthesized from the reaction of [Li][ATI] wit...