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The photocatalytic transformation of carbon dioxide (CO) into valuable chemicals is a challenging process that requires effective and selective catalysts. However, most polymer-based photocatalysts with electron donor-acceptor (D-A) structures are synthesized with a fixed D-A ratio by using expensive monomers. Herein, we report a simple strategy to prepare polyarene oxides (PAOs) with quinone structural units via oxidation treatment of polyarene (PA). The resultant PAOs show tunable D-A structures and electronic band positions depending on the degree of oxidation, which can catalyze the photoreduction of CO with water under visible light irradiation, generating CO as the sole carbonaceous product without H generation. Especially, the PAO with an oxygen content of 17.6% afforded the highest CO production rate of 161.9 μmol g h. It is verified that the redox transformation between quinone and phenolic hydroxyl in PAOs achieves CO photoreduction coupled with water oxidation. This study provides a facile way to access conjugated polymers with a tunable D-A structure and demonstrates that the resultant PAOs are promising photocatalysts for CO reduction.
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http://dx.doi.org/10.1021/acs.langmuir.4c00210 | DOI Listing |
Chemistry
August 2025
Institute for Green Science, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA, 15213, USA.
The electron transfer from naphthalene at an oxidized iron TAML species (TAML = tetraamido macrocyclic ligand) is a key step of its environmentally relevant deep degradation by hydrogen peroxide in water leading first to naphthoquinones which are further converted to smaller fragments. Other polycyclic arenes are also oxidized, often faster than naphthalene consistent with their lower ionization potentials than that of naphthalene.
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February 2025
Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences Shanghai 200032 China
An efficient Pd-catalyzed regioselective intramolecular aerobic oxidative dehydrocoupling of BH/CH between -carborane and arenes has been achieved with the construction of a series of five-, six- and seven-membered rings under mild reaction conditions. Control experiments indicate that B-H activation proceeds preferentially over the aryl C-H. These new polyarene-carborane conjugates have potential applications in materials as demonstrated by pyrene fused -carborane that exhibits unique dual-phase emission, intramolecular charge transfer (ICT), and aggregation-induced emission (AIE) properties.
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January 2025
Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222, United States.
We present the serendipitous discovery of an unusual dimer formed from anthracene-derived polyarenes. Unlike the typical oxidative coupling of substituted aromatic scaffolds, the reaction yielded a dearomatized enone dimer as the sole product. This dearomatized motif, notably, does not undergo the commonly observed rearomatization, and no biaryl products were detected.
View Article and Find Full Text PDFLangmuir
March 2024
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and Interface and Thermodynamics, Chinese Academy of Sciences (CAS), Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, CAS, Beijing 100190, P. R. C
The photocatalytic transformation of carbon dioxide (CO) into valuable chemicals is a challenging process that requires effective and selective catalysts. However, most polymer-based photocatalysts with electron donor-acceptor (D-A) structures are synthesized with a fixed D-A ratio by using expensive monomers. Herein, we report a simple strategy to prepare polyarene oxides (PAOs) with quinone structural units via oxidation treatment of polyarene (PA).
View Article and Find Full Text PDFChem Rev
February 2024
University of Regensburg, Institute of Inorganic Chemistry, 93040 Regensburg, Germany.
This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident.
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