{
  "abstract": "Hydrolyzed TiCl4–ligand systems capable of capturing atmospheric CO2 and converting it into reduced carbon products under ambient moisture and visible light exhibit an unexpected recurring feature: one or more Ti–Cl bonds persist after prolonged atmospheric exposure. Residual chloride is conventionally interpreted as incomplete hydrolysis preceding conversion to condensed Ti–O–Ti networks. The underlying Ti–OH/Ti–O photochemistry connects these systems to established TiO2 photocatalysis, but persistent Ti–Cl bonds and coordinated ligands prevent their simple description as incompletely formed TiO2. Here we propose a broader interpretation in which partial chloride retention is a structural control variable in the active material. By kinetically limiting extensive hydrolysis and condensation, retained chloride may preserve molecular or oligomeric titanium oxychloride–hydroxo species, maintain Lewis-acidic and exchangeable coordination sites, regulate the density and lifetime of Ti–OH groups, and support coexistence of multiple structural and redox generations. The nitrogen-containing ligands may be integral to this persistence: coordination to titanium can moderate hydrolysis and condensation, while ligand protonation can retain hydrolysis-generated acidity as local ligand–H+/Cl- ion pairs. Proton and chloride equivalents may therefore remain distributed among coordinated chloride, protonated ligands, Ti–OH···Cl environments, and more strongly hydrogen-bonded HCl-containing motifs. Such retention could establish a local proton–chloride reservoir and make individual hydrolysis and ligand-exchange steps dynamically reversible without implying global equilibrium. Related persistence of Zr–Cl bonds in zirconium–ligand CO2-capture systems suggests that chloride retention may be a broader feature of evolving Group 4 metal ensembles. The proposal distinguishes direct observations from mechanistic inference: persistent chloride-containing families support incomplete hydrolysis, whereas their roles in redox stabilization, proton-coupled electron transfer, self-repair, and catalytic turnover remain testable hypotheses. If confirmed, controlled partial chloride retention would constitute a design principle rather than a synthetic imperfection in this form of artificial photosynthesis.",
  "abstract_shown": true,
  "affiliations": [
    "Oakwood Consulting,",
    "Guangdong Technion Israel Institute of Technology"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Gregory G. Arzoumanidis",
      "orcid": "0000-0002-1491-3359"
    },
    {
      "affs": [
        1
      ],
      "name": "Michail Paraskevas"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/apb2k8wevc1xm.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009701/v1",
  "fulltext_url": null,
  "id": "apb2k8wevc1xm",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009701/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",
      "2105|Advanced Photocatalysis Techniques"
    ]
  ],
  "openalex": "W7215075504",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009701/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-30",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/apb2k8wevc1xm.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009701",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009701/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "Persistent Ti–Cl Bonds Direct Self-Organization in Titanium–Ligand Artificial Photosynthesis Systems",
  "title_text": "Persistent Ti–Cl Bonds Direct Self-Organization in Titanium–Ligand Artificial Photosynthesis Systems",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/apb2k8wevc1xm",
  "venue": "ChemRxiv",
  "versions": []
}