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Transient absorption spectroscopic measurements indicate very short excited\u2010state lifetimes and ultrafast intersystem crossing for <jats:bold>Re<jats:sub>1<\/jats:sub>Pc<\/jats:bold> and <jats:bold>Re<jats:sub>2<\/jats:sub>Pc<\/jats:bold>, which contains two [Re(CO)<jats:sub>3<\/jats:sub>]<jats:sup>+<\/jats:sup> units. The excited\u2010state properties are ascribed to efficient spin\u2013orbit coupling and large Franck\u2013Condon factors originating from the complexes\u2019 distorted structures, that is, unsymmetric coordination of [Re(CO)<jats:sub>3<\/jats:sub>]<jats:sup>+<\/jats:sup> unit(s), one of which was confirmed by single\u2010crystal X\u2010ray analysis of a symmetrically substituted Pc with two [Re(CO)<jats:sub>3<\/jats:sub>]<jats:sup>+<\/jats:sup> units. <jats:bold>Re<jats:sub>1<\/jats:sub>Pc<\/jats:bold> represents a promising red\u2010light\u2010driven photoCORM that can be applied in biological environments or therapeutic applications.<\/jats:p>","DOI":"10.1002\/chem.202200716","type":"journal-article","created":{"date-parts":[[2022,6,26]],"date-time":"2022-06-26T22:28:58Z","timestamp":1656282538000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["A Red\u2010Light\u2010Driven CO\u2010Releasing Complex: Photoreactivities and Excited\u2010State Dynamics of Highly Distorted Tricarbonyl Rhenium Phthalocyanines"],"prefix":"10.1002","volume":"28","author":[{"given":"Mengfei","family":"Wang","sequence":"first","affiliation":[{"name":"Institute of Industrial Science The University of Tokyo  4-6-1 Komaba, Meguro-ku Tokyo 153-8505 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2350-5330","authenticated-orcid":false,"given":"Kei","family":"Murata","sequence":"additional","affiliation":[{"name":"Institute of Industrial Science The University of Tokyo  4-6-1 Komaba, Meguro-ku Tokyo 153-8505 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yosuke","family":"Koike","sequence":"additional","affiliation":[{"name":"Institute of Industrial Science The University of Tokyo  4-6-1 Komaba, Meguro-ku Tokyo 153-8505 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2647-1439","authenticated-orcid":false,"given":"Gediminas","family":"Jonusauskas","sequence":"additional","affiliation":[{"name":"Univ. Bordeaux, CNRS, LOMA, UMR 5798  F-33400 Talence France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amaury","family":"Furet","sequence":"additional","affiliation":[{"name":"Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255  F-33400 Talence France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9278-1857","authenticated-orcid":false,"given":"Dario M.","family":"Bassani","sequence":"additional","affiliation":[{"name":"Univ. 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Hyogo 669-1337 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuushi","family":"Shimoda","sequence":"additional","affiliation":[{"name":"Department of Chemistry Faculty of Science Kyushu University  7-4-4 Motooka, Nishi-ku Fukuoka 819-0395 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6748-1337","authenticated-orcid":false,"given":"Kiyoshi","family":"Miyata","sequence":"additional","affiliation":[{"name":"Department of Chemistry Faculty of Science Kyushu University  7-4-4 Motooka, Nishi-ku Fukuoka 819-0395 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1724-2009","authenticated-orcid":false,"given":"Ken","family":"Onda","sequence":"additional","affiliation":[{"name":"Department of Chemistry Faculty of Science Kyushu University  7-4-4 Motooka, Nishi-ku Fukuoka 819-0395 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and Applications, Vols. I\u2013IV","author":"Leznoff C. C.","year":"1989"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr030206t"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900254z"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9003049"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja411016f"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC02151E"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp076118k"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC04625F"},{"key":"e_1_2_8_54_1","unstructured":"The importance of oxidation for CO release was also confirmed by electrochemical oxidation reactions. Under an N2atmosphere and an applied potential in the range of 1.3\u20131.6\u2005V for 2\u2005h CO was detected by GC. CO was considered to be released by removing an electron from the Re ion which decreases the \u03c0-back donation."},{"key":"e_1_2_8_55_1","unstructured":"The stability and CO-releasing activity of liposomalRe1Pcin water were investigated. Pcs were encapsulated in liposomes for applications to aqueous solutions and living cells.[46]Small unilamellar liposomes ofRe1Pcin 1 2-dipalmitoyl-sn-glycero-3-phosphorylcholine (DPPC) were prepared in accordance with the previously reported methods. The CW red-light-driven CO-releasing reaction ofRe1Pcwas proceeded even in water (Figure\u2005S5) while liposomalRe1Pcis stable in water in the absent of light irradiation (Figure\u2005S6)."},{"key":"e_1_2_8_56_1","unstructured":"The demetallation reaction ofRe2Pcin pyridine was reported previously.[47]"},{"key":"e_1_2_8_57_1","volume-title":"Handbook of Porphyrin Science Vol. 32","author":"Ishii K.","year":"2014"},{"key":"e_1_2_8_58_1","volume-title":"The Porphyrin Handbook Vol. 16","author":"Ishii K.","year":"2003"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201700668"},{"key":"e_1_2_8_60_1","unstructured":"ForIrPcCl(py)(D4hsymmetry of a \u03c0-conjugated system) the HOMO and nearly degenerate LUMOs are a1u(\u03c0) and egy(\u03c0*) (or egx(\u03c0*)) orbitals respectively. InRe1PcandRe2Pc whose \u03c0-conjugated systems deviate significantly fromD4hsymmetry owing to structural distortion the HOMO is predominantly a Pc-centred a1u-like \u03c0 orbital: this orbital is called the auorbital based on the approximation of the symmetry of \u03c0-conjugated system toD2hsymmetry. Also the LUMO and LUMO+1 correspond to the Pc-centred egy- and egx-like \u03c0* orbitals which are called the b3gand b2gorbitals respectively."},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00095a046"},{"key":"e_1_2_8_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100012a065"},{"key":"e_1_2_8_63_1","unstructured":"Based on its oxidation potential (+0.32\u2005V vs. Fc\/Fc+) reported in ref.\u2005[47] Re1Pcin the ground state cannot be oxidized by O2or1O2. Thus Re1Pcis considered to be oxidized in the excited-state."},{"key":"e_1_2_8_64_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202005042"},{"key":"e_1_2_8_65_1","unstructured":"Based on its oxidation potential (+0.74\u2005V vs. Fc\/Fc+) [58]a mononuclear ReItetraazaporphyrin complex (Re1TAP) oxidation is more difficult thanRe1Pcoxidation. Additionally Re1TAPdid not undergo photodecarbonylation under similar conditions. No spectral changes were observed in a solution containingRe1TAPin the presence of CW red light molecular oxygen and coordinative solvents (Figure\u2005S3b). These results are consistent with the mechanism proposed herein."},{"key":"e_1_2_8_66_1","unstructured":"Theoretical calculations were performed to investigate the oxidation ofRe1Pcin the T1state with molecular oxygen. 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