{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Arras J"],"funding":["Division of Chemistry","Division of Computer and Network Systems"],"pagination":["12943-12957"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC11256752"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["63(28)"],"pubmed_abstract":["Defined arrays of transition metal ions embedded in tailored polydentate ligand scaffolds allow for a systematic design of their physical properties. Such molecular strings of closed-shell transition metal centers are particularly interesting for Group 11 metal ions in the oxidation state +1 if they undergo metallophilic d<sup>10</sup>···d<sup>10</sup> contact interactions since these clusters are oftentimes efficient photoluminescence (PL) emitters. Copper is particularly attractive as a sustainable earth-abundant coinage metal source and because of the ability of several Cu<sup>I</sup> complexes to serve as powerful thermally activated delayed fluorescence (TADF) emitters in molecular/organic light-emitting devices (OLEDs). Our combined synthetic, crystallographic, photophysical, and computational study describes a straight tetracuprous array possessing a centrally disconnected Cu<sup>I</sup><sub>2</sub>···Cu<sup>I</sup><sub>2</sub> chain and a continuous helically bent Cu<sup>I</sup><sub>4</sub> complex. This molecular helix undergoes a facile rearrangement in diethyl ether solution, yielding an unprecedented nanosized Cu<sup>I</sup><sub>10</sub> cluster (2.9 × 2.0 nm) upon crystallization. All three clusters show either bright blue phosphorescence, TADF, or green/yellow multiband phosphorescence with quantum yields between 6.5 and 67%, which is persistent under hydrostatic pressure up to 30 kbar. Temperature-dependent PL investigations in combination with time-dependent density-functional theory (TD-DFT) calculations and void space analyses of the crystal packings complement a comprehensive correlation between the molecular structures and photoluminescence properties."],"journal":["Inorganic chemistry"],"pubmed_title":["Twisted and Disconnected Chains: Flexible Linear Tetracuprous Arrays and a Decanuclear Cu<sup>I</sup> Cluster as Blue- and Green/Yellow-Light Emitters."],"pmcid":["PMC11256752"],"funding_grant_id":["CHE-2155153","CHE-1800332","CNS-1920024"],"pubmed_authors":["Bhuvanesh N","Stollenz M","Lebedkin S","Gozem S","McMillen CD","Arras J","Calderon-Diaz A"],"additional_accession":[]},"is_claimable":false,"name":"Twisted and Disconnected Chains: Flexible Linear Tetracuprous Arrays and a Decanuclear Cu<sup>I</sup> Cluster as Blue- and Green/Yellow-Light Emitters.","description":"Defined arrays of transition metal ions embedded in tailored polydentate ligand scaffolds allow for a systematic design of their physical properties. Such molecular strings of closed-shell transition metal centers are particularly interesting for Group 11 metal ions in the oxidation state +1 if they undergo metallophilic d<sup>10</sup>···d<sup>10</sup> contact interactions since these clusters are oftentimes efficient photoluminescence (PL) emitters. Copper is particularly attractive as a sustainable earth-abundant coinage metal source and because of the ability of several Cu<sup>I</sup> complexes to serve as powerful thermally activated delayed fluorescence (TADF) emitters in molecular/organic light-emitting devices (OLEDs). Our combined synthetic, crystallographic, photophysical, and computational study describes a straight tetracuprous array possessing a centrally disconnected Cu<sup>I</sup><sub>2</sub>···Cu<sup>I</sup><sub>2</sub> chain and a continuous helically bent Cu<sup>I</sup><sub>4</sub> complex. This molecular helix undergoes a facile rearrangement in diethyl ether solution, yielding an unprecedented nanosized Cu<sup>I</sup><sub>10</sub> cluster (2.9 × 2.0 nm) upon crystallization. All three clusters show either bright blue phosphorescence, TADF, or green/yellow multiband phosphorescence with quantum yields between 6.5 and 67%, which is persistent under hydrostatic pressure up to 30 kbar. Temperature-dependent PL investigations in combination with time-dependent density-functional theory (TD-DFT) calculations and void space analyses of the crystal packings complement a comprehensive correlation between the molecular structures and photoluminescence properties.","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Jul","modification":"2025-04-04T03:20:15.059Z","creation":"2025-04-04T03:20:15.059Z"},"accession":"S-EPMC11256752","cross_references":{"pubmed":["38935842"],"doi":["10.1021/acs.inorgchem.4c01646"]}}