Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems
Abstract For the first time, the simultaneous synthesis and deposition of heterometallic porphyrin conjugated polymer thin films from a simple and scalable gas‐phase approach are reported. The oxidative chemical vapor deposition (oCVD) reaction of 5,15‐(diaryl) porphyrins chelated with different met...
| Main Authors: | , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2023-02-01
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| Series: | Advanced Materials Interfaces |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/admi.202202237 |
| _version_ | 1797730893626867712 |
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| author | Anna Lucia Pellegrino Giuseppe Bengasi Kamal Baba Drialys Cardenas‐Morcoso Deepak Bansal Graziella Malandrino Nicolas D. Boscher |
| author_facet | Anna Lucia Pellegrino Giuseppe Bengasi Kamal Baba Drialys Cardenas‐Morcoso Deepak Bansal Graziella Malandrino Nicolas D. Boscher |
| author_sort | Anna Lucia Pellegrino |
| collection | DOAJ |
| description | Abstract For the first time, the simultaneous synthesis and deposition of heterometallic porphyrin conjugated polymer thin films from a simple and scalable gas‐phase approach are reported. The oxidative chemical vapor deposition (oCVD) reaction of 5,15‐(diaryl) porphyrins chelated with different metal cations (M = Co(II), Ni(II), Zn(II), Cu(II), Pd(II)) readily yields the formation of new hetero‐metalated fused porphyrin tapes, such as evidenced by in‐depth high‐resolution mass spectrometry studies. The impact of the coreactants on the regioselectivity of the intermolecular dehydrogenative coupling reaction and the formation of double or triple bonds between the porphyrin units is demonstrated. The oCVD reaction of multiple porphyrins brings the possibility to easily engineer the chemical features and the electronic and optoelectronic properties of these highly conjugated porphyrin polymers. Particularly, it is demonstrated that porphyrin conjugated polymers having different chelated metal cations can achieve higher electrical conductivities and promote narrower bandgaps. The gas‐phase approach presented herein overcomes the main limitations of the conventional solution‐based approaches and opens the path to the engineering of a novel class donor–acceptor heterometallic polymers with high interest in several fields including multimetallic electrocatalysis, photocatalysis, sensing, and nonlinear optics applications. |
| first_indexed | 2024-03-12T11:50:48Z |
| format | Article |
| id | doaj.art-a4ddc09fb0ab4d8194f94c3be07bbd65 |
| institution | Directory Open Access Journal |
| issn | 2196-7350 |
| language | English |
| last_indexed | 2024-03-12T11:50:48Z |
| publishDate | 2023-02-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Advanced Materials Interfaces |
| spelling | doaj.art-a4ddc09fb0ab4d8194f94c3be07bbd652023-08-31T09:02:05ZengWiley-VCHAdvanced Materials Interfaces2196-73502023-02-01106n/an/a10.1002/admi.202202237Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin SystemsAnna Lucia Pellegrino0Giuseppe Bengasi1Kamal Baba2Drialys Cardenas‐Morcoso3Deepak Bansal4Graziella Malandrino5Nicolas D. Boscher6Materials Research and Technology Department Luxembourg Institute of Science and Technology 28 Avenue des Hauts‐Fourneaux Esch‐sur‐Alzette L‐4362 LuxembourgMaterials Research and Technology Department Luxembourg Institute of Science and Technology 28 Avenue des Hauts‐Fourneaux Esch‐sur‐Alzette L‐4362 LuxembourgMaterials Research and Technology Department Luxembourg Institute of Science and Technology 28 Avenue des Hauts‐Fourneaux Esch‐sur‐Alzette L‐4362 LuxembourgMaterials Research and Technology Department Luxembourg Institute of Science and Technology 28 Avenue des Hauts‐Fourneaux Esch‐sur‐Alzette L‐4362 LuxembourgMaterials Research and Technology Department Luxembourg Institute of Science and Technology 28 Avenue des Hauts‐Fourneaux Esch‐sur‐Alzette L‐4362 LuxembourgDipartimento di Scienze Chimiche Università di Catania INSTM UdR Catania Viale Andrea Doria 6 Catania 95125 ItalyMaterials Research and Technology Department Luxembourg Institute of Science and Technology 28 Avenue des Hauts‐Fourneaux Esch‐sur‐Alzette L‐4362 LuxembourgAbstract For the first time, the simultaneous synthesis and deposition of heterometallic porphyrin conjugated polymer thin films from a simple and scalable gas‐phase approach are reported. The oxidative chemical vapor deposition (oCVD) reaction of 5,15‐(diaryl) porphyrins chelated with different metal cations (M = Co(II), Ni(II), Zn(II), Cu(II), Pd(II)) readily yields the formation of new hetero‐metalated fused porphyrin tapes, such as evidenced by in‐depth high‐resolution mass spectrometry studies. The impact of the coreactants on the regioselectivity of the intermolecular dehydrogenative coupling reaction and the formation of double or triple bonds between the porphyrin units is demonstrated. The oCVD reaction of multiple porphyrins brings the possibility to easily engineer the chemical features and the electronic and optoelectronic properties of these highly conjugated porphyrin polymers. Particularly, it is demonstrated that porphyrin conjugated polymers having different chelated metal cations can achieve higher electrical conductivities and promote narrower bandgaps. The gas‐phase approach presented herein overcomes the main limitations of the conventional solution‐based approaches and opens the path to the engineering of a novel class donor–acceptor heterometallic polymers with high interest in several fields including multimetallic electrocatalysis, photocatalysis, sensing, and nonlinear optics applications.https://doi.org/10.1002/admi.202202237chemical vapor depositionD–A copolymersfused porphyrinsporphyrin conjugated polymersthin films |
| spellingShingle | Anna Lucia Pellegrino Giuseppe Bengasi Kamal Baba Drialys Cardenas‐Morcoso Deepak Bansal Graziella Malandrino Nicolas D. Boscher Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems Advanced Materials Interfaces chemical vapor deposition D–A copolymers fused porphyrins porphyrin conjugated polymers thin films |
| title | Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems |
| title_full | Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems |
| title_fullStr | Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems |
| title_full_unstemmed | Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems |
| title_short | Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems |
| title_sort | heterometallic porphyrin conjugated polymer thin films a gas phase approach for the engineering of new fused porphyrin systems |
| topic | chemical vapor deposition D–A copolymers fused porphyrins porphyrin conjugated polymers thin films |
| url | https://doi.org/10.1002/admi.202202237 |
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