Tetraaza[1.1.1.1]m,p,m,p‑cyclophane Diradical Dications Revisited: Tuning Spin States by Confronted Arenes

Diradical dications of two kinds of alternate-meta-para-linked tetraazacyclophanes in which p-phenylene (1) and 9,10-anthracenylene (2a) moieties are embedded in their macrocyclic backbones were successfully isolated as air-stable salts. The structures of 1 2+ and 2a 2+ were elucidated by X-ray anal...

Full description

Saved in:
Bibliographic Details
Published in:Organic letters 2017-06, Vol.19 (12), p.3115-3118
Main Authors: Kurata, Ryohei, Sakamaki, Daisuke, Ito, Akihiro
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-a411t-aa599e582d4c73d27470bc9b97cc8e94dbfba97d073d56abe7db9e46e7a20b9b3
cites cdi_FETCH-LOGICAL-a411t-aa599e582d4c73d27470bc9b97cc8e94dbfba97d073d56abe7db9e46e7a20b9b3
container_end_page 3118
container_issue 12
container_start_page 3115
container_title Organic letters
container_volume 19
creator Kurata, Ryohei
Sakamaki, Daisuke
Ito, Akihiro
description Diradical dications of two kinds of alternate-meta-para-linked tetraazacyclophanes in which p-phenylene (1) and 9,10-anthracenylene (2a) moieties are embedded in their macrocyclic backbones were successfully isolated as air-stable salts. The structures of 1 2+ and 2a 2+ were elucidated by X-ray analysis, and significantly different types of structural deformation led to different spin density distributions due to the steric demand of the confronted arene moieties. The singlet–triplet energy gaps were determined to be +0.3 kcal mol–1 (+151 K) and −1.0 kcal mol–1 (−503 K) by SQUID measurements, indicating the triplet ground state for 1 2+ and the singlet ground state for 2a 2+.
doi_str_mv 10.1021/acs.orglett.7b01229
format article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1905740903</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1905740903</sourcerecordid><originalsourceid>FETCH-LOGICAL-a411t-aa599e582d4c73d27470bc9b97cc8e94dbfba97d073d56abe7db9e46e7a20b9b3</originalsourceid><addsrcrecordid>eNp9kMtKAzEUhoMo3p9AkFm6aGuSmWkad1KvIAhaVyLDSeZUI9NkTDJCXfkKvqJPYrTVpYSQQ_L9J5yPkD1GB4xydgg6DJx_bDDGgVCUcS5XyCYred4XtOSrf_WQbpCtEJ4pZelGrpMNPioFy1m5SZoJRg_wBvds8LMeZr22l_bn-4ee68a1T2AxOzEeaqOhSZWGaJwN2Q2-mmAi1kfZpLPGPma3rbHZbYSIIVPzbOzs1DubiOzYo8WwQ9am0ATcXZ7b5O7sdDK-6F9dn1-Oj6_6UDAW-wCllFiOeF1okddcFIIqLZUUWo9QFrWaKpCipumxHIJCUSuJxRAFcKqkyrfJwaJv691LhyFWMxM0Nk0axXWhYpKWoqCS5gnNF6j2LgSP06r1ZgZ-XjFafWuukuZqqblaak6p_eUHnZph_Zf59ZqAwwXwnX52nbdp3n9bfgEZVo2T</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1905740903</pqid></control><display><type>article</type><title>Tetraaza[1.1.1.1]m,p,m,p‑cyclophane Diradical Dications Revisited: Tuning Spin States by Confronted Arenes</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Kurata, Ryohei ; Sakamaki, Daisuke ; Ito, Akihiro</creator><creatorcontrib>Kurata, Ryohei ; Sakamaki, Daisuke ; Ito, Akihiro</creatorcontrib><description>Diradical dications of two kinds of alternate-meta-para-linked tetraazacyclophanes in which p-phenylene (1) and 9,10-anthracenylene (2a) moieties are embedded in their macrocyclic backbones were successfully isolated as air-stable salts. The structures of 1 2+ and 2a 2+ were elucidated by X-ray analysis, and significantly different types of structural deformation led to different spin density distributions due to the steric demand of the confronted arene moieties. The singlet–triplet energy gaps were determined to be +0.3 kcal mol–1 (+151 K) and −1.0 kcal mol–1 (−503 K) by SQUID measurements, indicating the triplet ground state for 1 2+ and the singlet ground state for 2a 2+.</description><identifier>ISSN: 1523-7060</identifier><identifier>EISSN: 1523-7052</identifier><identifier>DOI: 10.1021/acs.orglett.7b01229</identifier><identifier>PMID: 28571315</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Organic letters, 2017-06, Vol.19 (12), p.3115-3118</ispartof><rights>Copyright © 2017 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a411t-aa599e582d4c73d27470bc9b97cc8e94dbfba97d073d56abe7db9e46e7a20b9b3</citedby><cites>FETCH-LOGICAL-a411t-aa599e582d4c73d27470bc9b97cc8e94dbfba97d073d56abe7db9e46e7a20b9b3</cites><orcidid>0000-0002-8698-0032</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27922,27923</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28571315$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kurata, Ryohei</creatorcontrib><creatorcontrib>Sakamaki, Daisuke</creatorcontrib><creatorcontrib>Ito, Akihiro</creatorcontrib><title>Tetraaza[1.1.1.1]m,p,m,p‑cyclophane Diradical Dications Revisited: Tuning Spin States by Confronted Arenes</title><title>Organic letters</title><addtitle>Org. Lett</addtitle><description>Diradical dications of two kinds of alternate-meta-para-linked tetraazacyclophanes in which p-phenylene (1) and 9,10-anthracenylene (2a) moieties are embedded in their macrocyclic backbones were successfully isolated as air-stable salts. The structures of 1 2+ and 2a 2+ were elucidated by X-ray analysis, and significantly different types of structural deformation led to different spin density distributions due to the steric demand of the confronted arene moieties. The singlet–triplet energy gaps were determined to be +0.3 kcal mol–1 (+151 K) and −1.0 kcal mol–1 (−503 K) by SQUID measurements, indicating the triplet ground state for 1 2+ and the singlet ground state for 2a 2+.</description><issn>1523-7060</issn><issn>1523-7052</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNp9kMtKAzEUhoMo3p9AkFm6aGuSmWkad1KvIAhaVyLDSeZUI9NkTDJCXfkKvqJPYrTVpYSQQ_L9J5yPkD1GB4xydgg6DJx_bDDGgVCUcS5XyCYred4XtOSrf_WQbpCtEJ4pZelGrpMNPioFy1m5SZoJRg_wBvds8LMeZr22l_bn-4ee68a1T2AxOzEeaqOhSZWGaJwN2Q2-mmAi1kfZpLPGPma3rbHZbYSIIVPzbOzs1DubiOzYo8WwQ9am0ATcXZ7b5O7sdDK-6F9dn1-Oj6_6UDAW-wCllFiOeF1okddcFIIqLZUUWo9QFrWaKpCipumxHIJCUSuJxRAFcKqkyrfJwaJv691LhyFWMxM0Nk0axXWhYpKWoqCS5gnNF6j2LgSP06r1ZgZ-XjFafWuukuZqqblaak6p_eUHnZph_Zf59ZqAwwXwnX52nbdp3n9bfgEZVo2T</recordid><startdate>20170616</startdate><enddate>20170616</enddate><creator>Kurata, Ryohei</creator><creator>Sakamaki, Daisuke</creator><creator>Ito, Akihiro</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-8698-0032</orcidid></search><sort><creationdate>20170616</creationdate><title>Tetraaza[1.1.1.1]m,p,m,p‑cyclophane Diradical Dications Revisited: Tuning Spin States by Confronted Arenes</title><author>Kurata, Ryohei ; Sakamaki, Daisuke ; Ito, Akihiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a411t-aa599e582d4c73d27470bc9b97cc8e94dbfba97d073d56abe7db9e46e7a20b9b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kurata, Ryohei</creatorcontrib><creatorcontrib>Sakamaki, Daisuke</creatorcontrib><creatorcontrib>Ito, Akihiro</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Organic letters</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kurata, Ryohei</au><au>Sakamaki, Daisuke</au><au>Ito, Akihiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Tetraaza[1.1.1.1]m,p,m,p‑cyclophane Diradical Dications Revisited: Tuning Spin States by Confronted Arenes</atitle><jtitle>Organic letters</jtitle><addtitle>Org. Lett</addtitle><date>2017-06-16</date><risdate>2017</risdate><volume>19</volume><issue>12</issue><spage>3115</spage><epage>3118</epage><pages>3115-3118</pages><issn>1523-7060</issn><eissn>1523-7052</eissn><abstract>Diradical dications of two kinds of alternate-meta-para-linked tetraazacyclophanes in which p-phenylene (1) and 9,10-anthracenylene (2a) moieties are embedded in their macrocyclic backbones were successfully isolated as air-stable salts. The structures of 1 2+ and 2a 2+ were elucidated by X-ray analysis, and significantly different types of structural deformation led to different spin density distributions due to the steric demand of the confronted arene moieties. The singlet–triplet energy gaps were determined to be +0.3 kcal mol–1 (+151 K) and −1.0 kcal mol–1 (−503 K) by SQUID measurements, indicating the triplet ground state for 1 2+ and the singlet ground state for 2a 2+.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>28571315</pmid><doi>10.1021/acs.orglett.7b01229</doi><tpages>4</tpages><orcidid>https://orcid.org/0000-0002-8698-0032</orcidid></addata></record>
fulltext fulltext
identifier ISSN: 1523-7060
ispartof Organic letters, 2017-06, Vol.19 (12), p.3115-3118
issn 1523-7060
1523-7052
language eng
recordid cdi_proquest_miscellaneous_1905740903
source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
title Tetraaza[1.1.1.1]m,p,m,p‑cyclophane Diradical Dications Revisited: Tuning Spin States by Confronted Arenes
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-14T13%3A20%3A09IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Tetraaza%5B1.1.1.1%5Dm,p,m,p%E2%80%91cyclophane%20Diradical%20Dications%20Revisited:%20Tuning%20Spin%20States%20by%20Confronted%20Arenes&rft.jtitle=Organic%20letters&rft.au=Kurata,%20Ryohei&rft.date=2017-06-16&rft.volume=19&rft.issue=12&rft.spage=3115&rft.epage=3118&rft.pages=3115-3118&rft.issn=1523-7060&rft.eissn=1523-7052&rft_id=info:doi/10.1021/acs.orglett.7b01229&rft_dat=%3Cproquest_cross%3E1905740903%3C/proquest_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a411t-aa599e582d4c73d27470bc9b97cc8e94dbfba97d073d56abe7db9e46e7a20b9b3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=1905740903&rft_id=info:pmid/28571315&rfr_iscdi=true