Modulating the Shape of Short Metal‐Mediated Heteroleptic Tapes of Porphyrins
In view of developing artificial light‐responsive complex systems, the preparation of discrete and robust heteroleptic assemblies of different chromophores in precisely defined positions is of great value since they would allow to investigate directional processes unavailable in symmetrical architec...
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Veröffentlicht in: | Chemistry : a European journal 2023-06, Vol.29 (36), p.e202300893-n/a |
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description | In view of developing artificial light‐responsive complex systems, the preparation of discrete and robust heteroleptic assemblies of different chromophores in precisely defined positions is of great value since they would allow to investigate directional processes unavailable in symmetrical architectures. Here we describe the preparation, through a modular stepwise approach, and characterization of four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes, labeled D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3 or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3 or 4′cisDPyMP=D4) through four {t,c,c‐RuCl2(CO)2} fragments. Whereas D4−T4−D4 is flat, the tapes containing at least one 3′PyP, i. e. D3−T4−D3, D4−T3−D4, and D3−T3−D3, have unprecedented – and well defined – 3D geometries, and each exists in solution as a pair of stereoisomers in slow conformational equilibrium. The X‐ray molecular structures of two such conformers, the C‐shaped (D3−T4−D3)C and the z‐shaped (D4−T3−D4)z, were determined and are fully consistent with the solution NMR findings.
As in a chemical conveyor belt, our stepwise synthetic approach afforded the four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3, or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3, or 4′cisDPyMP=D4) through four highly symmetrical {t,c,c‐RuCl2(CO)2} (Ru) fragments. |
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As in a chemical conveyor belt, our stepwise synthetic approach afforded the four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3, or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3, or 4′cisDPyMP=D4) through four highly symmetrical {t,c,c‐RuCl2(CO)2} (Ru) fragments.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202300893</identifier><identifier>PMID: 37067844</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Chemistry ; Chromophores ; Complex systems ; heteroleptic ; metal-mediated self-assembly ; Molecular structure ; NMR ; Nuclear magnetic resonance ; porphyrinoids ; Porphyrins ; Robustness ; ruthenium ; stepwise synthesis ; Stereoisomerism ; Stereoisomers</subject><ispartof>Chemistry : a European journal, 2023-06, Vol.29 (36), p.e202300893-n/a</ispartof><rights>2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH</rights><rights>2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.</rights><rights>2023. This article is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4133-8e2837025525f3dc2fdbcf66cfeb5480fa378a9198a2f75530b84cd242c87de23</citedby><cites>FETCH-LOGICAL-c4133-8e2837025525f3dc2fdbcf66cfeb5480fa378a9198a2f75530b84cd242c87de23</cites><orcidid>0000-0002-0007-0880 ; 0000-0002-4908-9400 ; 0000-0001-8641-0489 ; 0000-0003-0115-6560</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.202300893$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202300893$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/37067844$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Vidal, Alessio</creatorcontrib><creatorcontrib>Rossato, Daniel</creatorcontrib><creatorcontrib>Iengo, Elisabetta</creatorcontrib><creatorcontrib>Balducci, Gabriele</creatorcontrib><creatorcontrib>Alessio, Enzo</creatorcontrib><title>Modulating the Shape of Short Metal‐Mediated Heteroleptic Tapes of Porphyrins</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>In view of developing artificial light‐responsive complex systems, the preparation of discrete and robust heteroleptic assemblies of different chromophores in precisely defined positions is of great value since they would allow to investigate directional processes unavailable in symmetrical architectures. Here we describe the preparation, through a modular stepwise approach, and characterization of four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes, labeled D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3 or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3 or 4′cisDPyMP=D4) through four {t,c,c‐RuCl2(CO)2} fragments. Whereas D4−T4−D4 is flat, the tapes containing at least one 3′PyP, i. e. D3−T4−D3, D4−T3−D4, and D3−T3−D3, have unprecedented – and well defined – 3D geometries, and each exists in solution as a pair of stereoisomers in slow conformational equilibrium. The X‐ray molecular structures of two such conformers, the C‐shaped (D3−T4−D3)C and the z‐shaped (D4−T3−D4)z, were determined and are fully consistent with the solution NMR findings.
As in a chemical conveyor belt, our stepwise synthetic approach afforded the four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3, or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3, or 4′cisDPyMP=D4) through four highly symmetrical {t,c,c‐RuCl2(CO)2} (Ru) fragments.</description><subject>Chemistry</subject><subject>Chromophores</subject><subject>Complex systems</subject><subject>heteroleptic</subject><subject>metal-mediated self-assembly</subject><subject>Molecular structure</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>porphyrinoids</subject><subject>Porphyrins</subject><subject>Robustness</subject><subject>ruthenium</subject><subject>stepwise synthesis</subject><subject>Stereoisomerism</subject><subject>Stereoisomers</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqF0EFLwzAUB_AgipvTq0cpePHS-Zo0bXqUMZ2wMcF5Lln64jq6pSYtspsfwc_oJzFjc4IXLy_v8Mufx5-Qywj6EQC9VQtc9SlQBiAydkS6EadRyNKEH5MuZHEaJpxlHXLm3BIAsoSxU9JhKSSpiOMumU5M0VayKdevQbPA4HkhawyM9ouxTTDBRlZfH58TLErZYBGMsEFrKqybUgUzb90WPxlbLza2XLtzcqJl5fBi__bIy_1wNhiF4-nD4-BuHKo4YiwUSIU_gnJOuWaForqYK50kSuOcxwK0ZKmQWZQJSXXKOYO5iFVBY6pEWiBlPXKzy62teWvRNfmqdAqrSq7RtC6nAjzmPsvT6z90aVq79td5xSBOwE-v-julrHHOos5rW66k3eQR5Nuq823V-aFq_-FqH9vOV1gc-E-3HmQ78F5WuPknLh-MhpPf8G_mWIp4</recordid><startdate>20230627</startdate><enddate>20230627</enddate><creator>Vidal, Alessio</creator><creator>Rossato, Daniel</creator><creator>Iengo, Elisabetta</creator><creator>Balducci, Gabriele</creator><creator>Alessio, Enzo</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-0007-0880</orcidid><orcidid>https://orcid.org/0000-0002-4908-9400</orcidid><orcidid>https://orcid.org/0000-0001-8641-0489</orcidid><orcidid>https://orcid.org/0000-0003-0115-6560</orcidid></search><sort><creationdate>20230627</creationdate><title>Modulating the Shape of Short Metal‐Mediated Heteroleptic Tapes of Porphyrins</title><author>Vidal, Alessio ; Rossato, Daniel ; Iengo, Elisabetta ; Balducci, Gabriele ; Alessio, Enzo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4133-8e2837025525f3dc2fdbcf66cfeb5480fa378a9198a2f75530b84cd242c87de23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Chemistry</topic><topic>Chromophores</topic><topic>Complex systems</topic><topic>heteroleptic</topic><topic>metal-mediated self-assembly</topic><topic>Molecular structure</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>porphyrinoids</topic><topic>Porphyrins</topic><topic>Robustness</topic><topic>ruthenium</topic><topic>stepwise synthesis</topic><topic>Stereoisomerism</topic><topic>Stereoisomers</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Vidal, Alessio</creatorcontrib><creatorcontrib>Rossato, Daniel</creatorcontrib><creatorcontrib>Iengo, Elisabetta</creatorcontrib><creatorcontrib>Balducci, Gabriele</creatorcontrib><creatorcontrib>Alessio, Enzo</creatorcontrib><collection>Wiley Online Library (Open Access Collection)</collection><collection>Wiley Free Content</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Vidal, Alessio</au><au>Rossato, Daniel</au><au>Iengo, Elisabetta</au><au>Balducci, Gabriele</au><au>Alessio, Enzo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Modulating the Shape of Short Metal‐Mediated Heteroleptic Tapes of Porphyrins</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2023-06-27</date><risdate>2023</risdate><volume>29</volume><issue>36</issue><spage>e202300893</spage><epage>n/a</epage><pages>e202300893-n/a</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>In view of developing artificial light‐responsive complex systems, the preparation of discrete and robust heteroleptic assemblies of different chromophores in precisely defined positions is of great value since they would allow to investigate directional processes unavailable in symmetrical architectures. Here we describe the preparation, through a modular stepwise approach, and characterization of four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes, labeled D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3 or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3 or 4′cisDPyMP=D4) through four {t,c,c‐RuCl2(CO)2} fragments. Whereas D4−T4−D4 is flat, the tapes containing at least one 3′PyP, i. e. D3−T4−D3, D4−T3−D4, and D3−T3−D3, have unprecedented – and well defined – 3D geometries, and each exists in solution as a pair of stereoisomers in slow conformational equilibrium. The X‐ray molecular structures of two such conformers, the C‐shaped (D3−T4−D3)C and the z‐shaped (D4−T3−D4)z, were determined and are fully consistent with the solution NMR findings.
As in a chemical conveyor belt, our stepwise synthetic approach afforded the four novel and robust metal‐mediated heteroleptic 4+3 porphyrin tapes D4−T4−D4, D3−T4−D3, D4−T3−D4, and D3−T3−D3, where a central meso‐tetrapyridylporphyrin (either 3′‐TPyP=T3, or 4′‐TPyP=T4) is connected to two equal cis‐dipyridylporphyrins (either 3′cisDPyMP=D3, or 4′cisDPyMP=D4) through four highly symmetrical {t,c,c‐RuCl2(CO)2} (Ru) fragments.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>37067844</pmid><doi>10.1002/chem.202300893</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0002-0007-0880</orcidid><orcidid>https://orcid.org/0000-0002-4908-9400</orcidid><orcidid>https://orcid.org/0000-0001-8641-0489</orcidid><orcidid>https://orcid.org/0000-0003-0115-6560</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Chemistry Chromophores Complex systems heteroleptic metal-mediated self-assembly Molecular structure NMR Nuclear magnetic resonance porphyrinoids Porphyrins Robustness ruthenium stepwise synthesis Stereoisomerism Stereoisomers |
title | Modulating the Shape of Short Metal‐Mediated Heteroleptic Tapes of Porphyrins |
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