{
  "abstract": "We performed a comprehensive electrochemical and spectroelectrochemical study of three transition metal phthalocyanine (Pc) complexes, Pc n-OBu (2−)Mn III Cl, Pc tBu (2−)Mn III Cl and Pc tBu (2−)Cr III Cl (Pc tBu is the dianion of 2,9(10),16(17),23(24)-tetra- tert -butyl-phthalocyanine and Pc n-OBu is the dianion of 1,4,8,11,15,18,22,25-octa-n-butoxy-phthalocyanine), that are relevant for a variety of bond-breaking and forming reactions. Syntheses were optimized for previously reported tert -butylated species. Solvent-dependent voltammetry, spectroelectrochemistry, and for the first time for Mn III and Cr III Pc derivatives, spectroelectrochemical magnetic circular dichroism (MCD), were used to assess ligand- versus metal-centered redox events, electrochemical and chemical reversibilities of electron transfer, and effects of axial ligand coordination in dichloromethane or chloroform (DCM or CHCl 3 ) versus N,N -dimethylformamide (DMF). Comparisons are made to previously reported voltammetry and spectra of both Pc(2−)Mn II and chemically prepared oxidation states of Pc(2−)Cr II . We observe differences in localization of reduction events in P c n-OBu (2−)Mn III Cl versus Pc tBu (2−)Mn III Cl, with a more electron-rich ring promoting formation of MnI over Pc-centered reduction. We observe unique reduction behavior in Pc tBu (2−)Cr III Cl that points towards a mixture of ligand- and metal-centered character. To the best of our knowledge, these studies represent the first complete solvent-dependent spectroelectrochemical characterization of both Mn III and Cr III phthalocyanine derivatives across up to six different oxidation states.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "University of Tennessee",
    "Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, British Columbia, Canada, V5A 1S6"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Kelsie J. Tuggle"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Haleigh M. Grace"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Breanna E. Muldowney"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Ryan S. Arnold"
    },
    {
      "affs": [
        2
      ],
      "name": "Daniel B. Leznoff"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Viktor N. Nemykin"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Brendon J. McNicholas",
      "orcid": "0000-0002-3654-681X"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/11etbe73xmfgw.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008429/v1",
  "fulltext_url": null,
  "id": "11etbe73xmfgw",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008429/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2505|Porphyrin and Phthalocyanine Chemistry"
    ]
  ],
  "openalex": "W7211887478",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008429/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-07",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/11etbe73xmfgw.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008429",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008429/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2505|Porphyrin and Phthalocyanine Chemistry",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Potential-Dependent Redox Speciation in Substituted MnIII and CrIII Phthalocyanines",
  "title_text": "Potential-Dependent Redox Speciation in Substituted MnIII and CrIII Phthalocyanines",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/11etbe73xmfgw",
  "venue": "ChemRxiv",
  "versions": []
}