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The complexes contain two neutral tridendate dgpy ligands and in some cases [PF6]\u2212 ions form ion clusters with the positive manganese species, exhibiting different manganese oxidation states within the same ligand environment. While IR spectra assigned to Mn(II, III, IV) species show similar vibrational patterns, confirming largely metal-centered redox processes, a clearly different spectrum was observed for the in situ generated monocation [Mn(dgpy)2]+, raising the question of whether this complex contains a MnI central ion or a reduced ligand (dgpy)\u2022\u2013. Comparison of the spectroscopic data to the results of density functional theory (DFT) calculations using the CAM-B3LYP functional assigns its structure to a [MnII(dgpy)(dgpy)\u2022\u2013 ]+ configuration. This \u201cnon-innocent\u201d electronic behavior of the dgpy ligand in the gas phase is elucidated by electronic structure computations and attributed to the asymmetric, localized charge distribution of the extra electron on the pyridine moiety of only one of the dgpy ligands. The results demonstrate the novel perspectives offered by mass spectrometrically controlled gas phase spectroscopy for the generation, isolation, and characterization of unusual charge states of ligand-stabilized metal complexes.<\/jats:p>","DOI":"10.1021\/acs.jpca.6c02934","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:14:08Z","timestamp":1785849248000},"page":"6367-6378","source":"Crossref","is-referenced-by-count":0,"title":["Characterization\nof Manganese Oxidation States in\nDiguanidylpyridine Complexes by Vibrational Dissociation Spectroscopy\nand DFT Calculations"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-1695-1923","authenticated-orcid":true,"given":"Philipp","family":"Weber","sequence":"first","affiliation":[{"name":"RPTU Kaiserslautern-Landau , , Erwin Schro\u0308dinger Strasse 52 , ,","place":["Kaiserslautern, Germany, 67663"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maximilian E.","family":"Huber","sequence":"additional","affiliation":[{"name":"RPTU Kaiserslautern-Landau , , Erwin Schro\u0308dinger Strasse 52 , ,","place":["Kaiserslautern, Germany, 67663"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-9534-8744","authenticated-orcid":true,"given":"Adela","family":"Ceman","sequence":"additional","affiliation":[{"name":"RPTU Kaiserslautern-Landau , , Erwin Schro\u0308dinger Strasse 52 , ,","place":["Kaiserslautern, Germany, 67663"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9537-4117","authenticated-orcid":true,"given":"Jonathan","family":"Martens","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, The Netherlands, 6525 AJ"]},{"name":"HFML-FELIX , Toernooiveld 7 , ,","place":["Nijmegen, The Netherlands, 6525 ED"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jos","family":"Oomens","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, The Netherlands, 6525 AJ"]},{"name":"HFML-FELIX , Toernooiveld 7 , ,","place":["Nijmegen, The Netherlands, 6525 ED"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Giel","family":"Berden","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, The Netherlands, 6525 AJ"]},{"name":"HFML-FELIX , Toernooiveld 7 , ,","place":["Nijmegen, The Netherlands, 6525 ED"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7632-3437","authenticated-orcid":true,"given":"Christoph","family":"van Wu\u0308llen","sequence":"additional","affiliation":[{"name":"RPTU Kaiserslautern-Landau , , Erwin Schro\u0308dinger Strasse 52 , ,","place":["Kaiserslautern, Germany, 67663"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1483-4156","authenticated-orcid":true,"given":"Katja","family":"Heinze","sequence":"additional","affiliation":[{"name":"Johannes Gutenberg University Mainz , , Duesbergweg 10-14 , ,","place":["Mainz, Germany, 55218"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christoph","family":"Riehn","sequence":"additional","affiliation":[{"name":"RPTU Kaiserslautern-Landau , , Erwin Schro\u0308dinger Strasse 52 , ,","place":["Kaiserslautern, Germany, 67663"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1303-2370","authenticated-orcid":true,"given":"Jennifer","family":"Meyer","sequence":"additional","affiliation":[{"name":"RPTU Kaiserslautern-Landau , , Erwin Schro\u0308dinger Strasse 52 , ,","place":["Kaiserslautern, Germany, 67663"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,28]]},"reference":[{"key":"2026081308271158800_cit1","doi-asserted-by":"publisher","first-page":"5322","DOI":"10.1021\/cr300503r","article-title":"Visible Light Photoredox Catalysis\nwith Transition Metal Complexes: Applications in Organic Synthesis","volume":"113","author":"Prier","year":"2013","journal-title":"Chem. 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