{
  "abstract": "Charge-transfer (metal-to-ligand, MLCT, ligand-to-metal, LMCT, and interligand, (LLCT) and intraligand (π−π* and triplet-multiplet) transitions observed in the UV-vis-NIR and magnetic circular dichroism (MCD) spectra of high-spin Pc tBu Cr III Cl, Pc tBu Mn III Cl, and Pc OBu Mn III Cl (Pc tBu is the dianion of the 2,9(10),16(17),23(24)-tetra-tert-butyl-phthalocyanine and Pc OBu is the dianion of the 1,4,8,11,15,18,22,25-octa-n-butoxy-phthalocyanine) complexes were analyzed with the help of group theory combined with time-dependent density functional theory and ab initio (CASSCF and NEVPT2(13e,14o)) calculations. The energy shift between tert-butylated and butoxylated Pc rings, the energy shift between Mn and Cr centers, and the change in solvent donicity between dichloromethane/chloroform (DCM / CHCl 3 ) and N,N-dimethylformamide (DMF) were used to systematically perturb the energies of electronic transitions. It was demonstrated that the triplet-multiplet transitions dominate the NIR region of the UV-vis-NIR and MCD spectra, while LMCT bands dominate the “phthalocyanine window” (350-550 nm) region of the UV-vis-NIR and MCD spectra. Like other trivalent transition-metal phthalocyanines, MLCT transitions were predicted in the UV region of the UV-vis-NIR and MCD spectra. General trends in triplet-multiplet transitions across d 1 -d 9 configurations as well as the function of axial ligands for a given metal are delineated and parameterized. These studies will be used for further understanding of wavelength-dependent photochemical activity and the effects of structural substitutions on electrocatalytic and photocatalytic transformations.",
  "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": 9,
  "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": [
        0,
        1
      ],
      "name": "Emma E. Lane"
    },
    {
      "affs": [
        2
      ],
      "name": "Daniel B. Leznoff"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Konstantinos Vogiatzis"
    },
    {
      "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/c5n0vjtnefwpj.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008160/v1",
  "fulltext_url": null,
  "id": "c5n0vjtnefwpj",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008160/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": "W7213769119",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-20",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/c5n0vjtnefwpj.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008160",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008160/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2505|Porphyrin and Phthalocyanine Chemistry",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Deciphering Charge-Transfer and Triplet-Multiplet Excited States in Substituted MnIII and CrIII Phthalocyanines: Insights from UV-Vis-NIR, MCD, and Theory",
  "title_text": "Deciphering Charge-Transfer and Triplet-Multiplet Excited States in Substituted MnIII and CrIII Phthalocyanines: Insights from UV-Vis-NIR, MCD, and Theory",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/c5n0vjtnefwpj",
  "venue": "ChemRxiv",
  "versions": []
}