{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T19:11:36Z","timestamp":1791227496227,"version":"4.1.0"},"reference-count":89,"publisher":"Wiley","issue":"30","license":[{"start":{"date-parts":[[2010,6,30]],"date-time":"2010-06-30T00:00:00Z","timestamp":1277856000000},"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":[[2010,8,9]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Two families of dyad and triad systems based on perylene monoimide (PMI), quaterthiophene (QT), and 9,10\u2010bis(1,3\u2010dithiol\u20102\u2010ylidene)\u20109,10\u2010dihydroanthracene (extended tetrathiafulvalene, exTTF) molecular components have been designed and synthesized. The dyads (<jats:bold>D1<\/jats:bold> and <jats:bold>D2<\/jats:bold>) are of the PMI\u2013QT type and the triads (<jats:bold>T1<\/jats:bold> and <jats:bold>T2<\/jats:bold>) of the PMI\u2013QT\u2013exTTF type. The two families differ in the saturated or unsaturated nature of the linker groups (ethynylene in <jats:bold>D1<\/jats:bold> and <jats:bold>T1<\/jats:bold>, ethylene in <jats:bold>D2<\/jats:bold> and <jats:bold>T2<\/jats:bold>) that bridge the molecular components. The dyads and triads have been characterized by electrochemical, photophysical, and computational methods. Both the experimental and the computational (DFT) results indicate that in the unsaturated systems strong intercomponent interactions lead to substantial perturbation of the properties of the subunits. In particular, in <jats:bold>T1<\/jats:bold>, delocalization is particularly effective between the QT and exTTF units, which would be better viewed combined as a single electronic subsystem. For the dyad systems, the photophysics observed following excitation of the PMI unit is solvent\u2010dependent. In moderately polar solvents (dichloromethane, diethyl ether) fast charge separation is followed by recombination to the ground state. In toluene, slow conversion to the charge\u2010separated state is followed by intersystem crossing and recombination to yield the triplet state of the PMI unit. The behavior of the triads, on the other hand, is remarkably similar to that of the corresponding dyads, which indicates that, after primary charge separation, hole shift from the oxidized QT component to exTTF is quite inefficient. This unexpected result has been rationalized on the basis of the anomalous (simultaneous two\u2010electron oxidation) electrochemistry of exTTF and with the help of DFT calculations. In fact, although exTTF is electrochemically easier to oxidize than QT by around 0.6\u2005V, the one\u2010electron redox orbitals (HOMOs) of the two units in triad <jats:bold>T2<\/jats:bold> are almost degenerate.<\/jats:p>","DOI":"10.1002\/chem.201000640","type":"journal-article","created":{"date-parts":[[2010,7,2]],"date-time":"2010-07-02T09:01:42Z","timestamp":1278061302000},"page":"9140-9153","source":"Crossref","is-referenced-by-count":21,"title":["Hole\u2010Transfer Dyads and Triads Based on Perylene Monoimide, Quaterthiophene, and Extended Tetrathiafulvalene"],"prefix":"10.1002","volume":"16","author":[{"given":"Julien","family":"Boixel","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Errol","family":"Blart","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yann","family":"Pellegrin","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fabrice","family":"Odobel","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicola","family":"Perin","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Claudio","family":"Chiorboli","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sandro","family":"Fracasso","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marcella","family":"Ravaglia","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Franco","family":"Scandola","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2010,7,30]]},"reference":[{"key":"e_1_2_5_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.200700087"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0504598102"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0506694103"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature01209"},{"key":"e_1_2_5_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/B800582F"},{"key":"e_1_2_5_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/b203780g"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/B417580H"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700026t"},{"key":"e_1_2_5_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527618248"},{"key":"e_1_2_5_10_2","volume-title":"Supramolecular 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fact a small residual emission (intensity ca. 10\u2009% of that of the model) is observed. On the basis of its unquenched lifetime (5\u2005ns) this emission is attributed to an impurity of free PMI."},{"key":"e_1_2_5_57_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.432142"},{"key":"e_1_2_5_58_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-93116-1"},{"key":"e_1_2_5_59_2","doi-asserted-by":"publisher","DOI":"10.1016\/0304-4173(85)90014-X"},{"key":"e_1_2_5_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00330a004"},{"key":"e_1_2_5_61_2","unstructured":"With the appropriate parameters (see the Supporting Information) the solvent contribution to the reorganizational energy is estimated to be about 0.6\u2005eV in dichloromethane."},{"key":"e_1_2_5_62_2","unstructured":"The energy of the charge\u2010separated state in diethyl ether can be estimated by using Equation\u2005(1) (using appropriate effective ionic radii see the Supporting Information) to be ca. 1.96\u2005eV."},{"key":"e_1_2_5_63_2","unstructured":"Note that a decrease in solvent polarity does not only increase the energy of the charge\u2010separated state but it also decreases the reorganizational energy of the processes. In the inverted region the two factors act synergistically to reduce the rates whereas in the normal regime partial compensation between the two effects should be expected."},{"key":"e_1_2_5_64_2","unstructured":"The energy of the charge\u2010separated state in toluene can be estimated by using Equation\u2005(1) (using appropriate effective ionic radii see the Supporting Information) to be ca. 2.29\u2005eV."},{"key":"e_1_2_5_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp7109516"},{"key":"e_1_2_5_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja000219d"},{"key":"e_1_2_5_67_2","unstructured":"\u00a0"},{"key":"e_1_2_5_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo034432e"},{"key":"e_1_2_5_69_2","doi-asserted-by":"publisher","DOI":"10.1039\/B603149H"},{"key":"e_1_2_5_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo9719416"},{"key":"e_1_2_5_71_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20010302)7:5<973::AID-CHEM973>3.0.CO;2-#"},{"key":"e_1_2_5_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr068066l"},{"key":"e_1_2_5_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/la0611460"},{"key":"e_1_2_5_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja062358m"},{"key":"e_1_2_5_75_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_5_76_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp013949w"},{"key":"e_1_2_5_77_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_5_78_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4757-0887-5_1"},{"key":"e_1_2_5_79_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1674902"},{"key":"e_1_2_5_80_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(80)85347-4"},{"key":"e_1_2_5_81_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00533485"},{"key":"e_1_2_5_82_2","doi-asserted-by":"publisher","DOI":"10.1080\/00268977400100171"},{"key":"e_1_2_5_83_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1672392"},{"key":"e_1_2_5_84_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1677527"},{"key":"e_1_2_5_85_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.455064"},{"key":"e_1_2_5_86_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp000156l"},{"key":"e_1_2_5_87_2","unstructured":"Gaussian\u200503 Revision C.02 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery \u2005Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone B. Mennucci M. Cossi G. Scalmani N. Rega G.\u2005A. Petersson H. Nakatsuji M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai M. Klene X. Li J.\u2005E. Knox H.\u2005P. Hratchian J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski P.\u2005Y. Ayala K. Morokuma G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg V.\u2005G. Zakrzewski S. Dapprich A.\u2005D. Daniels M.\u2005C. Strain O. Farkas D.\u2005K. Malick A.\u2005D. Rabuck K. Raghavachari J.\u2005B. Foresman J.\u2005V. Ortiz Q. Cui A.\u2005G. Baboul S. Clifford J. Cioslowski B.\u2005B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R.\u2005L. Martin D.\u2005J. Fox T. Keith M.\u2005A. Al\u2010Laham C.\u2005Y. Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong C. Gonzalez J.\u2005A. Pople Gaussian Inc. Wallingford CT 2004."},{"key":"e_1_2_5_88_2","unstructured":"Extensive work has been performed by Guldi and Martin[8 \u200935 \u200938\u201340 \u200967]on dyads in which fullerene is a photoexcited electron acceptor and exTTF is the electron donor. For these systems with an intrinsically larger driving force (0.7\u2005eV using the experimental two\u2010electron value) the problem of the effective one\u2010electron oxidation potential of exTTF is evidently much less critical than here."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201000640","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201000640","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:15:51Z","timestamp":1760267751000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201000640"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2010,7,30]]},"references-count":89,"journal-issue":{"issue":"30","published-print":{"date-parts":[[2010,8,9]]}},"alternative-id":["10.1002\/chem.201000640"],"URL":"https:\/\/doi.org\/10.1002\/chem.201000640","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2010,7,30]]}}}