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Electrochemical measurements show the presence of electronic interactions between the two external Fe<jats:sup>II<\/jats:sup>\u2005atoms of the <jats:italic>cis\u2010<\/jats:italic> and <jats:italic>trans<\/jats:italic>\u2010isomeric complexes <jats:italic>cis<\/jats:italic>\/<jats:italic>trans<\/jats:italic>\u2010<jats:bold>1<\/jats:bold>[PF<jats:sub>6<\/jats:sub>]<jats:sub>2<\/jats:sub>. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT\/\/DFT calculations. As expected, both mixed valence complexes <jats:italic>cis<\/jats:italic>\/<jats:italic>trans<\/jats:italic>\u2010<jats:bold>1<\/jats:bold>[PF<jats:sub>6<\/jats:sub>]<jats:sub>3<\/jats:sub> exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru<jats:sup>II<\/jats:sup>\u2010CN\u2010Fe<jats:sup>II<\/jats:sup> subunit to a Fe<jats:sup>III<\/jats:sup> d\u2005orbital with some contributions from the co\u2010ligands. Moreover, the NIR transition energy in <jats:italic>trans<\/jats:italic>\u2010<jats:bold>1<\/jats:bold>[PF<jats:sub>6<\/jats:sub>]<jats:sub>3<\/jats:sub> is lower than that in <jats:italic>cis<\/jats:italic>\u2010<jats:bold>1<\/jats:bold>[PF<jats:sub>6<\/jats:sub>]<jats:sub>3<\/jats:sub>, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two\u2010electron oxidized complexes show that <jats:italic>trans<\/jats:italic>\u2010<jats:bold>1<\/jats:bold>[PF<jats:sub>6<\/jats:sub>]<jats:sub>4<\/jats:sub> possesses lower vicinal Ru<jats:sup>II<\/jats:sup>\u2192Fe<jats:sup>III<\/jats:sup> MMCT transition energy than <jats:italic>cis<\/jats:italic>\u2010<jats:bold>1<\/jats:bold>[PF<jats:sub>6<\/jats:sub>]<jats:sub>4<\/jats:sub>. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the <jats:italic>cis<\/jats:italic> and <jats:italic>trans<\/jats:italic> complexes can be well rationalized using TDDFT\/\/DFT calculations.<\/jats:p>","DOI":"10.1002\/chem.201303195","type":"journal-article","created":{"date-parts":[[2014,4,25]],"date-time":"2014-04-25T13:09:02Z","timestamp":1398431342000},"page":"7025-7036","source":"Crossref","is-referenced-by-count":42,"title":["Influence of Central Metalloligand Geometry on Electronic Communication between Metals: Syntheses, Crystal Structures, MMCT Properties of Isomeric Cyanido\u2010Bridged Fe<sub>2<\/sub>Ru Complexes, and TDDFT Calculations"],"prefix":"10.1002","volume":"20","author":[{"given":"Xiao","family":"Ma","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chen\u2010Sheng","family":"Lin","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sheng\u2010Min","family":"Hu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chun\u2010Hong","family":"Tan","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yue\u2010Hong","family":"Wen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tian\u2010Lu","family":"Sheng","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xin\u2010Tao","family":"Wu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,4,25]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja027219t"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20001016)112:20<3766::AID-ANGE3766>3.0.CO;2-S"},{"key":"e_1_2_6_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20001016)39:20<3620::AID-ANIE3620>3.0.CO;2-T"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature08301"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200904674"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200904674"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature00790"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja101887f"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar970007u"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1098\/rsta.2007.2138"},{"key":"e_1_2_6_11_2","unstructured":"\u00a0"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201208023"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201202225"},{"key":"e_1_2_6_13_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201202225"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1455"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201000765"},{"key":"e_1_2_6_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201000765"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200906264"},{"key":"e_1_2_6_16_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200906264"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201105987"},{"key":"e_1_2_6_17_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201105987"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja077527x"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1038\/363058a0"},{"key":"e_1_2_6_20_2","unstructured":"\u00a0"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.08.008"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.09.005"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.09.007"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2012.10.021"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100441k"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9003852"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2006.06.003"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200602737"},{"key":"e_1_2_6_28_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200602737"},{"key":"e_1_2_6_29_2","first-page":"424","volume":"35","author":"D\u2032Alessandro D. 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