{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T03:33:42Z","timestamp":1790912022685,"version":"4.1.0"},"reference-count":191,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2008,11,14]],"date-time":"2008-11-14T00:00:00Z","timestamp":1226620800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2008,12,19]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Ground\u2010state (GS) and excited\u2010state (ES) properties of novel photomagnetic molecular devices (PMMDs) are investigated by means of density functional theory. These organic PMMDs undergo a ferromagnetic alignment of their intramolecular spins in the lowest ES. They are comprised of: 1)\u2005an anthracene unit (An) as both the photosensitizer (P) and a transient spin carrier (SC) in the triplet ES (<jats:sup>3<\/jats:sup>An*); 2)\u2005imino\u2010nitroxyl (IN) or oxoverdazyl (OV) stable radical(s) as the dangling SC(s); and 3)\u2005bridge(s) (B) connecting peripheral SC(s) to the An core at positions 9 and 10. Improving the efficiency of the PMMDs involves strengthening the ES intramolecular exchange coupling (<jats:italic>J<jats:sub>ES<\/jats:sub><\/jats:italic>) between transient and persistent SCs, hence the choice of 2\u2010pyrimidinyl (pm) as B elements to replace the original <jats:italic>p<\/jats:italic>\u2010phenylene (ph). Dissymmetry of the pm connectors leads to [SC\u2010B\u2010P\u2010B\u2010SC] regio\u2010isomers <jats:italic>int<\/jats:italic>. and <jats:italic>ext.,<\/jats:italic> depending on whether the pyrimidinic nitrogen atoms point towards the An core or the peripheral SCs, respectively. For the <jats:italic>int<\/jats:italic>. regio\u2010isomers we show that the photoinduced spin alignment is significantly improved because the <jats:italic>J<jats:sub>ES<\/jats:sub><\/jats:italic>\/<jats:italic>k<\/jats:italic><jats:sub>B<\/jats:sub> value is increased by a factor of more than two compared with the ph\u2010based analogue (<jats:italic>J<jats:sub>ES<\/jats:sub><\/jats:italic>\/<jats:italic>k<\/jats:italic><jats:sub>B<\/jats:sub>&gt;+400\u2005K). Most importantly, we show that the optimal <jats:italic>J<jats:sub>ES<\/jats:sub><\/jats:italic>\/<jats:italic>k<\/jats:italic><jats:sub>B<\/jats:sub> value (\u2248+600\u2005K) could be reached in the event of an unexpected saddle\u2010shaped structural distortion of the lowest ES. Accounting for this intriguing behavior requires dissection of the combined effects of 1)\u2005borderline intramolecular steric hindrance about key An\u2013pm linkages, which translates into the flatness of the potential energy surface; 2)\u2005spin density disruption due to the presence of radicals; and 3)\u2005possibly intervening photochemistry, with An acting as a light\u2010triggered electron donor while pm, IN, and OV behave as electron acceptors. Finally, potentialities attached to the [(SC)\u2010pm\u2010An\u2010pm]<jats:sub>int<\/jats:sub> pattern are disclosed.<\/jats:p>","DOI":"10.1002\/chem.200801405","type":"journal-article","created":{"date-parts":[[2008,11,14]],"date-time":"2008-11-14T07:27:25Z","timestamp":1226647645000},"page":"11385-11405","source":"Crossref","is-referenced-by-count":29,"title":["Reaching Optimal Light\u2010Induced Intramolecular Spin Alignment within Photomagnetic Molecular Device Prototypes"],"prefix":"10.1002","volume":"14","author":[{"given":"Ilaria","family":"Ciofini","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carlo","family":"Adamo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yoshio","family":"Teki","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fabien","family":"Tuy\u00e8ras","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Philippe\u2005P.","family":"Lain\u00e9","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2008,12,12]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"Selected recent references:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/B514736K"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/b300075n"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/B607187B"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo060225d"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-009-3979-0_1"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)88348-4"},{"key":"e_1_2_6_9_2","volume-title":"Supramolecular Photochemistry","author":"Balzani V.","year":"1991"},{"key":"e_1_2_6_10_2","unstructured":"\u00a0"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19881000110"},{"key":"e_1_2_6_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198800891"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19901021117"},{"key":"e_1_2_6_12_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199013041"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac199062081457"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00028a006"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200401150"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja058357w"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic060679t"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0482278"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20020715)8:14<3162::AID-CHEM3162>3.0.CO;2-6"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja011069p"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/a901237k"},{"key":"e_1_2_6_22_2","doi-asserted-by":"crossref","unstructured":"P.\u2005P. 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Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong C. Gonzalez and J.\u2005A. Pople Gaussian Pittsburgh PA 2003."},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.478522"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.77.3865"},{"key":"e_1_2_6_55_2","first-page":"1976","author":"Dunning T. H.","journal-title":"Modern Theoretical Chemistry"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1677527"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01328601"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1098\/rspa.1929.0094"},{"key":"e_1_2_6_59_2","volume-title":"The Theory of Electric and Magnetic Susceptibilities","author":"Vleck J. H. 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The only additional antiferromagnetic contribution attached to the saddle\u2010shaped distortion is at first glance related to enhanced through\u2010space polarization interaction of remote SCs within triads. Indeed structure optimization indicates that the edge\u2010to\u2010edge distance is shortened by \u224810\u201315\u2009% in the saddle\u2010shaped conformation with respect to the axially distorted one (for instance the distance between oxygen termini is reduced from 22.22 to 19.20\u2005\u00c5 in the typical case ofTd7*). 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These parentages are in line with issues previously derived from structural magnetic and electronic analyses."},{"key":"e_1_2_6_107_2","unstructured":"The relaxed axially distorted conformation of mono\u2010reduced [Ref5]\u2212lies 0.08\u2005eV above the saddle\u2010shaped one with\u03b81=39.2\u00b0 versus 23.1\u00b0 for the folded conformation. Regarding the reduced reference regio\u2010isomerext. that is [Ref6]\u2212 the axially distorted conformation is by far the most stable conformation by at least 0.47\u2005eV (Figure S\u2009VI). 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