Catalytic Synthesis of Conjugated Azopolymers from Aromatic Diazides.
04 Mar 2021-Journal of the American Chemical Society (American Chemical Society)-Vol. 143, Iss: 10, pp 3975-3982
TL;DR: In this paper, a dinickel catalyzed N=N coupling reaction of aromatic diazides was used to synthesize polymers containing main chain azoarene repeat units.
Abstract: Conjugated polymers containing main chain azoarene repeat units are synthesized by a dinickel catalyzed N=N coupling reaction of aromatic diazides. The polymerization exhibits broad substrate scope...
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TL;DR: In this article , a strategy to synthesize covalent organic frameworks with azo linkage is presented. But it has not yet been exploited as a linkage of COFs, and it is not yet a suitable linkage chemistry for COFs.
Abstract: Exploring new linkage chemistry for covalent organic frameworks (COFs) provides a strong driving force to promote the development of this emerging class of crystalline porous organic materials. Herein we report a strategy to synthesize COFs with azo linkage, one of the most important functional unit in materials science but having not yet been exploited as a linkage of COFs. This strategy is developed on the basis of in situ linker exchange, by which imine-linked COFs are completely transformed into azo-linked COFs (Azo-COFs). Moreover, distinct properties of Azo-COFs from their corresponding imine-linked precursors are observed, indicating unique property of Azo-COFs. This strategy provides a useful approach to develop new linkage chemistry for COFs. It also has established a synthetic method for azo-linked COFs, which not only enriches the family of COFs but also offers a platform to explore properties and applications of this class of crystalline porous conjugated polymers.
25 citations
TL;DR: In this article, the authors explore the use of direct arylation polymerization (DArP) for conjugated polymers as an effective approach compared to conventional cross-coupling polymerizations.
Abstract: Simple and efficient methods are a key consideration for small molecule and polymer syntheses. Direct arylation polymerization (DArP) is of increasing interest for preparing conjugated polymers as an effective approach compared to conventional cross-coupling polymerizations. As DArP sees broader utilization, advancements are needed to access materials with improved properties and different monomer structures and to improve the scalability of conjugated polymer synthesis. Presented herein are considerations for developing new methods of conjugated polymer synthesis from small molecule transformations, exploring how DArP has successfully used this approach, and presenting how emerging polymerization methodologies are developing similarly. While it is common to adapt small molecule methods to polymerizations, we demonstrate the ways in which information gained from studying polymerizations can inform and inspire greater advancements in small molecule transformations. This circular approach to organic synthetic method development underlines the value of collaboration between small molecule and polymer-based synthetic research groups.
19 citations
TL;DR: In this article, a series of dinickel complexes supported by naphthyridine-diimine (NDI) ligands are investigated, and it is shown that these complexes can promote a broad range of two-electron redox processes in which the NDI ligand manages electron equivalents while the metals remain in a Ni(I)-Ni(I) state.
Abstract: Redox reactions that take place in enzymes and on the surfaces of heterogeneous catalysts often require active sites that contain multiple metals. By contrast, there are very few homogeneous catalysts with multinuclear active sites, and the field of organometallic chemistry continues to be dominated by the study of single metal systems. Multinuclear catalysts have the potential to display unique properties owing to their ability to cooperatively engage substrates. Furthermore, direct metal-to-metal covalent bonding can give rise to new electronic configurations that dramatically impact substrate binding and reactivity. In order to effectively capitalize on these features, it is necessary to consider strategies to avoid the dissociation of fragile metal-metal bonds in the course of a catalytic cycle. This Account describes one approach to accomplishing this goal using binucleating redox-active ligands.In 2006, Chirik showed that pyridine-diimines (PDI) have sufficiently low-lying π* levels that they can be redox-noninnocent in low-valent iron complexes. Extending this concept, we investigated a series of dinickel complexes supported by naphthyridine-diimine (NDI) ligands. These complexes can promote a broad range of two-electron redox processes in which the NDI ligand manages electron equivalents while the metals remain in a Ni(I)-Ni(I) state.Using (NDI)Ni2 catalysts, we have uncovered cases where having two metals in the active site addresses a problem in catalysis that had not been adequately solved using single-metal systems. For example, mononickel complexes are capable of stoichiometrically dimerizing aryl azides to form azoarenes but do not turn over due to strong product inhibition. By contrast, dinickel complexes are effective catalysts for this reaction and avoid this thermodynamic sink by binding to azoarenes in their higher-energy cis form.Dinickel complexes can also activate strong bonds through the cooperative action of both metals. Norbornadiene has a ring-strain energy that is similar to that of cyclopropane but is not prone to undergoing C-C oxidative addition with monometallic complexes. Using an (NDI)Ni2 complex, norbornadiene undergoes rapid ring opening by the oxidative addition of the vinyl and bridgehead carbons. An inspection of the resulting metallacycle reveals that it is stabilized through a network of secondary Ni-π interactions. This reactivity enabled the development of a catalytic carbonylative rearrangement to form fused bicyclic dienones.These vignettes and others described in this Account highlight some of the implications of metal-metal bonding in promoting a challenging step in a catalytic cycle or adjusting the thermodynamic landscape of key intermediates. Given that our studies have focused nearly exclusively on the (NDI)Ni2 system, we anticipate that many more such cases are left to be discovered as other transition-metal combinations and ligand classes are explored.
13 citations
TL;DR: In this paper , a dinucleating PNNP expanded pincer ligand was proposed to enable metal-metal cooperativity (MMC) and chemical non-innocence.
Abstract: Several metalloenzymes, including [FeFe]-hydrogenase, employ cofactors wherein multiple metal atoms work together with surrounding ligands that mediate heterolytic and concerted proton-electron transfer (CPET) bond activation steps. Herein, we report a new dinucleating PNNP expanded pincer ligand, which can bind two low-valent iron atoms in close proximity to enable metal-metal cooperativity (MMC). In addition, reversible partial dearomatization of the ligand's naphthyridine core enables both heterolytic metal-ligand cooperativity (MLC) and chemical non-innocence through CPET steps. Thermochemical and computational studies show how a change in ligand binding mode can lower the bond dissociation free energy of ligand C(sp3)-H bonds by ∼25 kcal mol-1. H-atom abstraction enabled trapping of an unstable intermediate, which undergoes facile loss of two carbonyl ligands to form an unusual paramagnetic (S = ) complex containing a mixed-valent iron(0)-iron(i) core bound within a partially dearomatized PNNP ligand. Finally, cyclic voltammetry experiments showed that these diiron complexes show catalytic activity for the electrochemical hydrogen evolution reaction. This work presents the first example of a ligand system that enables MMC, heterolytic MLC and chemical non-innocence, thereby providing important insights and opportunities for the development of bimetallic systems that exploit these features to enable new (catalytic) reactivity.
12 citations
TL;DR: In this article , the authors synthesized elemental skeletons composed of robust π-conjugated systems including two boron-fused azo groups, which showed an intense emission in the red or near-infrared (NIR) region both in solution and solid states.
Abstract: Development of novel near-infrared (NIR) emitters is essential for satisfying the growing demands of advancing optical telecommunication and medical technology. We synthesized elemental skeletons composed of robust π-conjugated systems including two boron-fused azo groups, which showed an intense emission in the red or near-infrared (NIR) region both in solution and solid states. Two types of bisboron complexes with different aromatic linkers showed emission properties with larger bathochromic shifts and emission efficiencies in solution than the corresponding monoboron complex. Transient absorption spectroscopy disclosed that the inferior optical properties of the monoboron complex can be attributed to fast nonradiative deactivation accompanied by a large structural relaxation after photoexcitation. The expanded π-conjugated system through multiple boron-fused azo groups can contribute to rigid molecular skeletons followed by improved emission properties. Moreover, the anti-form of the bisboron complex with fluorine groups in the opposite directions to the π-plane exhibited crystallization-induced emission enhancement in the NIR region. The molecular design by using multiple boron-fused azo groups is expected to be a critical strategy for creating novel NIR emitters.
11 citations
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Abstract: The field of chemical sensing is becoming ever more dependent upon novel materials. Polymers, crystals, glasses, particles, and nanostructures have made a profound impact and have endowed modern sensory systems with superior performance. Electronic polymers have emerged as one of the most important classes of transduction materials; they readily transform a chemical signal into an easily measured electrical or optical event. Although our group reviewed this field in 2000,1 the high levels of activity and the impact of these methods now justify a subsequent review as part of this special issue. In this review we restrict our discussions to purely fluorescence-based methods using conjugated polymers (CPs). We further confine our detailed coverage to articles published since our previous review and will only detail earlier research in this Introduction to illustrate fundamental concepts and terminology that underpin the recent literature.
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TL;DR: School of Chemistry, Bio21 Institute, University of Melbourne, 30 Flemington Road, Victoria 3010, Australia; School of Materials Science and Engineering, Nanyang Technological University, Nastyang Avenue, Republic of Singapore 639798; Institute of Materials Research and Engineering (IMRE) and the Agency for Science, Technology and Research (A*STAR), 3 Research Link, Singapore 117602.
Abstract: A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.
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TL;DR: In this article, a review of π-conjugated polymeric semiconductors for organic thin-film (or field effect) transistors (OTFTs or OFETs) and bulk-heterojunction photovoltaic (or solar) cell (BHJ-OPV or OSC) applications are summarized and analyzed.
Abstract: The optoelectronic properties of polymeric semiconductor materials can be utilized for the fabrication of organic electronic and photonic devices. When key structural requirements are met, these materials exhibit unique properties such as solution processability, large charge transporting capabilities, and/or broad optical absorption. In this review recent developments in the area of π-conjugated polymeric semiconductors for organic thin-film (or field-effect) transistors (OTFTs or OFETs) and bulk-heterojunction photovoltaic (or solar) cell (BHJ-OPV or OSC) applications are summarized and analyzed.
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TL;DR: This critical review details the studies completed to date on the 3 main classes of azobenzene derivatives and explains the mechanism behind the isomerization mechanism.
Abstract: Azobenzene undergoes trans → cisisomerization when irradiated with light tuned to an appropriate wavelength. The reverse cis →transisomerization can be driven by light or occurs thermally in the dark. Azobenzene's photochromatic properties make it an ideal component of numerous molecular devices and functional materials. Despite the abundance of application-driven research, azobenzene photochemistry and the isomerization mechanism remain topics of investigation. Additional substituents on the azobenzene ring system change the spectroscopic properties and isomerization mechanism. This critical review details the studies completed to date on the 3 main classes of azobenzene derivatives. Understanding the differences in photochemistry, which originate from substitution, is imperative in exploiting azobenzene in the desired applications.
2,062 citations