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With the aim of producing a photomechanical material for incorporation in soft microrobots, a one-dimensional diene coordination polymer (CP) [Cd(F-bpeb)(3-CBA)] (CP1, F-bpeb=4,4'-((1E,1'E)-(2,5-difluoro-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine, 3-HCBA=3-chlorobenzoic acid) was synthesized and characterized. Irradiation of CP1 with ultraviolet (UV) or visible light causes [2+2] photocycloaddition reactions resulting in the introduction of crystal strain which triggers various types of crystal movements. Composite films of CP1-PVA (SC) fabricated by dispersing CP1 crystals into polyvinyl alcohol (PVA) solution allow amplification of the crystal movement so that the film strips exhibit fast and flexible curling upon photoirradiation. The composite films may be cut into long rectangular strips and folded to simulate soft microrobots which exhibit a variety of fast, flexible and continuous photomechanical movements resembling a human performing various gymnastic exercises.
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http://dx.doi.org/10.1002/anie.202409472 | DOI Listing |
Acc Chem Res
September 2025
XStruct, Department of Chemistry, Ghent University, Krijgslaan-281, Building S3, B-9000 Ghent, Belgium.
Nat Commun
August 2025
Henan Key Laboratory of Natural Medicine Innovation and Transformation, Henan University, Kaifeng, Henan, PR China.
Asymmetric dearomative photocycloaddition has emerged as a transformative strategy for the enantioselective construction of complex three-dimensional molecular architectures from simple planar aromatic precursors. While significant progress has been made in this field, the scope has largely been confined to electron-rich and electron-neutral aromatic systems. Herein, we present a breakthrough with the development of the direct asymmetric dearomative photocycloaddition involving electron-deficient isoquinolines.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Frontiers Science Center for New Organic Matter, State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, P.R. China.
In this journal, a Correspondence by Ventura, Cozzi, and Ceroni reported time-resolved absorption spectroscopy studies in the electron transfer process from cyanoarene photocatalyst 3,4,5,6-tetrakis(diphenyl amino)phthalonitrile (4DPAPN) in the presence of tetrabutylammonium oxalate (TBAOx). This was used as a model reaction to investigate the mechanism of consecutive photoinduced electron transfer (ConPET) in our previously reported asymmetric [3+2] photocycloaddition. They proposed a new electron transfer pathway in which the electron from the excited state of the radical anion 4DPAPN* solvated in acetonitrile.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai 200433, China.
Although three different modes of photocycloaddition between arenes and alkenes are well-known, the control of reaction selectivity remains a long-standing challenge. In this study, we present the first tunable photocycloaddition of 1-naphthol derivatives under visible light irradiation, affording , , and cycloadducts, respectively. The success of the reaction hinges on a rational design of naphthalene substrates and the judicious selection of solvents and sensitizer.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Organisch-Chemisches Institut, Universität Münster, Corrensstraße 36, Münster 48149, Germany.
Visible-light-mediated energy transfer (EnT) photocatalysis has emerged as a highly appealing strategy for converting planar (hetero)arenes into complex, medicinally relevant, three-dimensional (3D) architectures. Current methodologies for intermolecular dearomative photocycloadditions, however, are restricted to bicyclic (hetero)aromatic systems, while the more abundant monocyclic (hetero)arenes remain vastly underexplored. Accessing the triplet state of the ubiquitous monocyclic (hetero)arenes poses a formidable challenge due to their high triplet energy barriers.
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