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By using the reaction of a double-decker homoleptic\/heteroleptic phthalocyanine samarium compound with metal-free phthalocyanine and cadmium acetate in 1,2,4-trichlorobenzene at 200 \u00b0C, two novel quintuple-decker heteroleptic phthalocyanine heterometallic samarium\u2013cadmium compounds, {(Pc)\u00adSm\u00ad(Pc)\u00adCd\u00ad(Pc*)\u00adCd\u00ad(Pc)\u00adSm\u00ad(Pc)} (1) and {(Pc)\u00adSm\u00ad(Pc*)\u00adCd\u00ad(Pc*)\u00adCd\u00ad(Pc*)\u00adSm\u00ad(Pc)} (2), together with one homoleptic phthalocyanine species, {(Pc*)\u00adSm\u00ad(Pc*)\u00adCd\u00ad(Pc*)\u00adCd\u00ad(Pc*)\u00adSm\u00ad(Pc*)} (3), were successfully fabricated, where H2Pc and H2Pc* represent unsubstituted phthalocyanine and 2,3,9,10,16,17,23,24-octakis\u00ad(n-pentyloxy)\u00adphthalocyanine, respectively. Their quintuple-decker structures have been disclosed by various spectroscopic techniques and single-crystal X-ray diffraction. In addition, valence tautomerization of these three quintuple-decker complexes has been achieved by the addition of phenoxathiin hexachloroantimonate, giving three oxidized forms including one-, two-, and three-electron oxidation products. From 1 to 3 with the same oxidation state, the increased number of n-pentyloxy substituents of phthalocyanine ligands induces the blue shift of electronic absorption in the IR region due to the increased gap associated with the introduction of electron-donating substituents. In particular, the electronic absorption spectra of one- and two-electron oxidation products for 1 exhibit a rare band in the middle-IR region around 3000 nm, being one of the farthest electronic transitions captured by UV\u2013vis spectroscopy. The three-electron oxidation product of 1 displays two bands at 2231 and 2740 nm, respectively. These data are well confirmed by IR spectroscopic data and theoretical calculation results.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.0c02816","type":"journal-article","created":{"date-parts":[[2020,11,13]],"date-time":"2020-11-13T16:46:01Z","timestamp":1605285961000},"page":"17591-17599","source":"Crossref","is-referenced-by-count":9,"title":["Quintuple-Decker Heteroleptic Phthalocyanine Heterometallic\nSamarium\u2013Cadmium Complexes. Synthesis, Crystal Structure, Electrochemical\nBehavior, and Spectroscopic Investigation"],"prefix":"10.1021","volume":"59","author":[{"given":"Chao","family":"Liu","sequence":"first","affiliation":[{"name":"University of Science and Technology Beijing , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei","family":"Yang","sequence":"additional","affiliation":[{"name":"University of Science and Technology Beijing , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8510-5033","authenticated-orcid":true,"given":"Yuexing","family":"Zhang","sequence":"additional","affiliation":[{"name":"Hubei University , , ,","place":["Wuhan, China, 430062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4263-9211","authenticated-orcid":true,"given":"Jianzhuang","family":"Jiang","sequence":"additional","affiliation":[{"name":"University of Science and Technology Beijing , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2020,11,13]]},"reference":[{"key":"2026081720285302300_cit1a","doi-asserted-by":"publisher","first-page":"724","DOI":"10.1016\/j.chempr.2017.10.005","article-title":"Flexible\nField-Effect Transistor-Type Sensors Based on Conjugated\nMolecules","volume":"3","author":"Lee","year":"2017","journal-title":"Chem."},{"key":"2026081720285302300_cit1b","doi-asserted-by":"publisher","first-page":"1319","DOI":"10.1002\/adma.201304346","article-title":"25th Anniversary Article: Organic Field-Effect Transistors:\nThe Path Beyond Amorphous Silicon","volume":"26","author":"Sirringhaus","year":"2014","journal-title":"Adv. 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