{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,27]],"date-time":"2025-10-27T15:58:27Z","timestamp":1761580707438,"version":"build-2065373602"},"reference-count":109,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2009,7,31]],"date-time":"2009-07-31T00:00:00Z","timestamp":1248998400000},"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":[[2009,9,14]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We report the synthesis and the characterizations of a novel dyad composed of a zinc porphyrin (ZnP) linked to a gold porphyrin (AuP) through an ethynyl spacer. The UV\/Vis absorption spectrum and the electrochemical properties clearly reveal that this dyad exhibits a strong electronic coupling in the ground state as evidenced by shifted redox potentials and the appearance of an intense charge\u2010transfer band localized at <jats:italic>\u03bb<\/jats:italic>=739\u2005nm in dichloromethane. A spectroelectrochemical study of the dyad along with the parent homometallic system (i.e., ZnP\u2013ZnP and AuP\u2013AuP) was undertaken to determine the spectra of the reduced and oxidized porphyrin units. Femtosecond transient absorption spectroscopic analysis showed that the photoexcitation of the heterometallic dyad leads to an ultrafast formation of a charge\u2010separated state (<jats:sup>+<\/jats:sup>ZnP\u2013AuP<jats:sup>.<\/jats:sup>) that displays a particularly long lifetime (<jats:italic>\u03c4<\/jats:italic>=4\u2005ns in toluene) for such a short separation distance. The molecular orbitals of the dyad were determined by DFT quantum\u2010chemical calculations. This theoretical study confirms that the observed intense band at <jats:italic>\u03bb<\/jats:italic>=739\u2005nm corresponds to an interporphyrin charge\u2010transfer transition from the HOMO orbital localized on the zinc porphyrin to LUMO orbitals localized on the gold porphyrin. Finally, a Hyper\u2013Rayleigh scattering study shows that the dyad possesses a large first molecular hyperpolarizability coefficient (<jats:italic>\u03b2<\/jats:italic>=2100\u00d710<jats:sup>\u221230<\/jats:sup>\u2005esu at <jats:italic>\u03bb<\/jats:italic>=1064\u2005nm), thus highlighting the valuable nonlinear optical properties of this new type of push\u2013pull porphyrin system.<\/jats:p>","DOI":"10.1002\/chem.200900262","type":"journal-article","created":{"date-parts":[[2009,7,31]],"date-time":"2009-07-31T09:04:10Z","timestamp":1249031050000},"page":"9058-9067","source":"Crossref","is-referenced-by-count":36,"title":["Charge\u2010Transfer State and Large First Hyperpolarizability Constant in a Highly Electronically Coupled Zinc and Gold Porphyrin Dyad"],"prefix":"10.1002","volume":"15","author":[{"given":"J\u00e9r\u00f4me","family":"Fortage","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Annabelle","family":"Scarpaci","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lydie","family":"Viau","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yann","family":"Pellegrin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Errol","family":"Blart","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Magnus","family":"Falkenstr\u00f6m","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Leif","family":"Hammarstr\u00f6m","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Inge","family":"Asselberghs","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ruben","family":"Kellens","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wim","family":"Libaers","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Koen","family":"Clays","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mattias\u2005P.","family":"Eng","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fabrice","family":"Odobel","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,9,3]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527603220"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature00791"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/35046000"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/a902659b"},{"volume-title":"Nonlinear Optical Properties of Organic Molecules and Crystals, Vol. 2","year":"1987","key":"e_1_2_6_5_2"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja952690q"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja952690q"},{"volume-title":"Electron Transfer\u2010From Isolated Molecules to Biomolecules","year":"1999","author":"Jortner J.","key":"e_1_2_6_8_2"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200603046"},{"key":"e_1_2_6_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200603046"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/b708318a"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja021278p"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp044261x"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0445847"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm034358g"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1038\/415767a"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.281.5383.1653"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/b704499b"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0735655"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.2178790"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0445847"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200703852"},{"key":"e_1_2_6_21_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200703852"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/b709859f"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0625150"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp067930a"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0645640"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja066376f"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic961016m"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-1409(199901)3:1<5::AID-JPP98>3.0.CO;2-N"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00078a081"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)61655-6"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(00)01102-9"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0520525"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1039\/b204265g"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1039\/b109915a"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0030140"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja993241j"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9922330"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20000717)112:14<2552::AID-ANGE2552>3.0.CO;2-7"},{"key":"e_1_2_6_38_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20000717)39:14<2451::AID-ANIE2451>3.0.CO;2-P"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(20000515)112:10<1888::AID-ANGE1888>3.0.CO;2-2"},{"key":"e_1_2_6_39_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(20000515)39:10<1818::AID-ANIE1818>3.0.CO;2-E"},{"key":"e_1_2_6_40_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0301-0104(99)00238-4"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1039\/a904209a"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1039\/a800992i"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9810078"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1039\/a801031e"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)91871-9"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.8178169"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.19950010913"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja962403y"},{"key":"e_1_2_6_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9939587"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja020651q"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0203925"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja030674k"},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0402553"},{"key":"e_1_2_6_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja061897o"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0009976"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971090126"},{"key":"e_1_2_6_56_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199701351"},{"key":"e_1_2_6_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo971736q"},{"key":"e_1_2_6_58_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo980098o"},{"key":"e_1_2_6_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo981488d"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39940001707"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(02)00494-X"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1039\/b516725f"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo971597c"},{"key":"e_1_2_6_64_2","doi-asserted-by":"publisher","DOI":"10.1039\/B513848E"},{"key":"e_1_2_6_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1522-2675(19981111)81:11<1964::AID-HLCA1964>3.0.CO;2-I"},{"journal-title":"The Porphyrin Handbook","year":"1999","author":"Kadish K. M.","key":"e_1_2_6_66_2"},{"key":"e_1_2_6_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00121a052"},{"key":"e_1_2_6_68_2","unstructured":"\u00a0"},{"key":"e_1_2_6_69_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200701335"},{"key":"e_1_2_6_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic800727e"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00492a044"},{"key":"e_1_2_6_72_2","first-page":"237","volume":"21","author":"Chambron J.\u2010C.","year":"1997","journal-title":"New J. Chem."},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200600161"},{"key":"e_1_2_6_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100181a001"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr941180w"},{"key":"e_1_2_6_76_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470166314.ch9"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1039\/B205620H"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50194a028"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9605663"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00069a047"},{"key":"e_1_2_6_81_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0119907"},{"key":"e_1_2_6_82_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp054420s"},{"key":"e_1_2_6_83_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50218a062"},{"key":"e_1_2_6_84_2","doi-asserted-by":"publisher","DOI":"10.1039\/b109795d"},{"key":"e_1_2_6_85_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1674902"},{"key":"e_1_2_6_86_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.448799"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.448800"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.448975"},{"key":"e_1_2_6_89_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_6_91_2","doi-asserted-by":"publisher","DOI":"10.1139\/p80-159"},{"key":"e_1_2_6_92_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(96)00440-X"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.475855"},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.477483"},{"key":"e_1_2_6_95_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1394921"},{"key":"e_1_2_6_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9716997"},{"key":"e_1_2_6_97_2","unstructured":"Gaussian 03 Revision D.02 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery J. Vreven T. K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Lyengar 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_6_98_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1590951"},{"key":"e_1_2_6_99_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0449399"},{"key":"e_1_2_6_100_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.66.2980"},{"key":"e_1_2_6_101_2","first-page":"455","volume":"85","author":"Clays K.","year":"1993","journal-title":"Adv. Chem. Phys."},{"key":"e_1_2_6_102_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1142538"},{"key":"e_1_2_6_103_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1148926"},{"key":"e_1_2_6_104_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(98)00795-7"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200900262","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200900262","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T18:29:49Z","timestamp":1760293789000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200900262"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,9,3]]},"references-count":109,"journal-issue":{"issue":"36","published-print":{"date-parts":[[2009,9,14]]}},"alternative-id":["10.1002\/chem.200900262"],"URL":"https:\/\/doi.org\/10.1002\/chem.200900262","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"type":"print","value":"0947-6539"},{"type":"electronic","value":"1521-3765"}],"subject":[],"published":{"date-parts":[[2009,9,3]]}}}