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The ITO electrode was submitted to a surface sol\u2013gel process with titanium <jats:italic>n<\/jats:italic>\u2010butoxide in order to deposit a titanium monolayer. Subsequently, porphyrins were assembled as monolayers on the titanium\u2010treated ITO surface via phosphonate, isophthalate, and thiolate groups. Slipped\u2010cofacial porphyrin dimers, the so\u2010called artificial special pair at the photoreaction center, were organized through imidazolyl\u2010to\u2010zinc complementary coordination of imidazolylporphyrinatozinc(<jats:sc>II<\/jats:sc>) units, which were covalently immobilized by ring\u2010closing olefin metathesis of allyl side chains. The modified surfaces were analyzed by means of X\u2010ray photoelectron spectroscopy. Photoirradiation of the porphyrin dimer generated a large anodic photocurrent in aqueous electrolyte solution containing hydroquinone as an electron sacrificer, due to the small reorganization energy of the dimer. The use of different linker groups led to significant differences in the efficiencies of anodic photocurrent generation. The apparent flat\u2010band potentials evaluated from the photocurrent properties at various pH values and under biased conditions imply that the band structure of the ITO electrode is modified by the anchoring species. The quantum yield for the anodic photocurrent generation by photoexcitation at the Soret band is increased to 15\u2009%, a surprisingly high value without a redox cascade structure on the ITO electrode surface, while excitation at the Q band is not so significant. Extensive exploration of the photocurrent properties has revealed that hot injection of the photoexcited electron from the S<jats:sub>2<\/jats:sub> level into the conduction band of the ITO electrode takes place before internal conversion to the S<jats:sub>1<\/jats:sub>* state, through the strong electronic communication of the phosphonyl anchor with the sol\u2013gel\u2010modified ITO surface.<\/jats:p>","DOI":"10.1002\/chem.200600304","type":"journal-article","created":{"date-parts":[[2006,9,15]],"date-time":"2006-09-15T04:58:24Z","timestamp":1158296304000},"page":"8123-8135","source":"Crossref","is-referenced-by-count":27,"title":["Efficient Charge Injection from the S<sub>2<\/sub> Photoexcited State of Special\u2010Pair Mimic Porphyrin Assemblies Anchored on a Titanium\u2010Modified ITO Anode"],"prefix":"10.1002","volume":"12","author":[{"given":"Mitsuhiko","family":"Morisue","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Noriko","family":"Haruta","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dipak","family":"Kalita","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yoshiaki","family":"Kobuke","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2006,10,19]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0268462"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-4095(199906)11:8<605::AID-ADMA605>3.0.CO;2-Q"},{"key":"e_1_2_6_3_2","unstructured":"\u00a0"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(98)00350-9"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0379-6779(00)00728-1"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja025673r"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp046337v"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja050481s"},{"key":"e_1_2_6_10_2","unstructured":"\u00a0"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja983204c"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1055745"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja045243w"},{"key":"e_1_2_6_14_2","unstructured":"SAMs on Au electrodes:"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja970945p"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002154k"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm049322i"},{"key":"e_1_2_6_18_2","unstructured":"SAMs on ITO electrodes:"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja034913f"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400377"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja044847x"},{"key":"e_1_2_6_22_2","unstructured":"Langmuir\u2013Blodgett films:"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-6090(85)90459-6"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-6090(89)90052-7"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/la981527g"},{"key":"e_1_2_6_26_2","unstructured":"Layer\u2010by\u2010layer membranes:"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20001103)112:21<4052::AID-ANGE4052>3.0.CO;2-Q"},{"key":"e_1_2_6_27_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20001103)39:21<3905::AID-ANIE3905>3.0.CO;2-Q"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja015596k"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja011700m"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1039\/b400027g"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/la047845z"},{"key":"e_1_2_6_32_2","volume-title":"Physics of Semiconductor Devices","author":"Sze S. 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