{
  "abstract": "Ion-pair complexes, in which an organic cation exists entirely in the second coordination sphere of an anionic metal complex, represent a structurally and electronically distinct compound class, whose solution behavior is influenced by solvent polarity and hydrogen-bonding interactions. Their capacity to undergo ion pair charge transfer (IPCT) transitions makes them attractive model complexes for ion-pairing equilibria and potential active species in catalytic cycles. Herein we report the synthesis, structural characterization, spectroscopic investigation and catalytic evaluation of the oxidorhenate(v) outer-sphere ion pair complexes (H2L1)[ReOCl3(L1)] (1) and (H2L2)[ReOCl3(L2)] (2). Both complexes crystallize as contact ion pairs stabilized by N–H⋯Cl and O–H⋯Cl hydrogen bonds. The hydrogen-bond-accepting Re–Cl bonds are significantly elongated as shown by single crystal X-ray diffraction analysis, indicating enhanced lability at these sites. Both complexes display a striking solvatochromism, assigned by UV/Vis spectroscopy to an IPCT transition operative exclusively in apolar media (λmax = 555 nm, ε = 2700 L mol−1 cm−1 for 1; λmax = 577 nm, ε = 920 L mol−1 cm−1 for 2, solvent: CHCl3). Additionally, DFT calculations across a series of solvents establish the thermodynamic basis for the observed solvent-dependent ion-pair equilibria. Cyclic voltammetry reveals quasi-reversible Re(v/vi) couples for 1 in both solvents and for 2 in MeCN (E1/2 = +0.431 V for 1; +0.258 V for 2 in MeCN vs. Fc+/Fc). Both complexes catalyze perchlorate reduction with dimethyl sulfide, achieving 92% conversion (TOF 0.37 h−1) for 1 and 55% (TOF 0.22 h−1) for 2. 1H NMR monitoring shows that 1 is not converted into the bis-chelate complex during catalysis.",
  "abstract_shown": true,
  "affiliations": [
    "Institute of Chemistry, University of Graz Schubertstraße 1 8010 Graz Austria",
    "Innovation Center of the Faculty of Chemistry, Belgrade Studentski trg 12-16 11158 Belgrade Serbia"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 9,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Tobias A. Doliner",
      "orcid": "0009-0004-7805-1446"
    },
    {
      "affs": [
        0
      ],
      "name": "Anna M. Schlegl"
    },
    {
      "affs": [
        0
      ],
      "name": "Kristin Kogler"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Milan Milovanović"
    },
    {
      "affs": [
        0
      ],
      "name": "A. D. Boese",
      "orcid": "0000-0001-7388-778X"
    },
    {
      "affs": [
        0
      ],
      "name": "Ferdinand Belaj",
      "orcid": "0000-0001-9749-2109"
    },
    {
      "affs": [
        0
      ],
      "name": "Antoine Dupé",
      "orcid": "0000-0001-7781-0771"
    },
    {
      "affs": [
        0
      ],
      "name": "Peter E. Hartmann",
      "orcid": "0000-0003-1148-5536"
    },
    {
      "affs": [
        0
      ],
      "name": "Jörg A. Schachner",
      "orcid": "0000-0002-1863-4680"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/7xvd55jb7td5b.bib",
  "cited_by": 0,
  "doi": "10.1039/d6dt02275h",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13712253/",
  "id": "7xvd55jb7td5b",
  "issns": [
    "1477-9226",
    "1477-9234"
  ],
  "landing_url": "https://doi.org/10.1039/d6dt02275h",
  "language": "en",
  "licence": "CC-BY-3.0",
  "licence_label": "CC BY 3.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/3.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Chemistry"
    ],
    [
      "openalex",
      "1606|Photochemistry and Electron Transfer Studies"
    ]
  ],
  "openalex": "W7223987669",
  "pdf_url": "https://pubs.rsc.org/dt/article-pdf/doi/10.1039/d6dt02275h/14957074/d6dt02275h.pdf",
  "pmcid": "PMC13712253",
  "pmid": "42937685",
  "published": "2026-10-27",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/7xvd55jb7td5b.ris",
  "sources": [
    {
      "first_seen": "2026-10-31T12:22:52Z",
      "native_id": "PMC13712253",
      "source": "pmc",
      "url": "https://doi.org/10.1039/d6dt02275h"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1606|Photochemistry and Electron Transfer Studies",
      "subfield": "physical"
    }
  ],
  "title": "Ion-pair complexes of oxidorhenate(v) with phenolate–oxazoline ligands: synthesis, solvatochromism and catalytic properties",
  "title_text": "Ion-pair complexes of oxidorhenate(v) with phenolate–oxazoline ligands: synthesis, solvatochromism and catalytic properties",
  "type": "peer-reviewed",
  "updated_at": "2026-10-31T12:22:52Z",
  "url": "https://research.draconitic.com/paper/7xvd55jb7td5b",
  "venue": "Dalton Transactions (Cambridge, England : 2003)",
  "versions": []
}