{"doi":"10.1021/acs.jpcc.5c08246","title":"Strategic Lifetime Tuning of Visible-Light Absorbing Two-Coordinate Metal Complexes","abstract":"This paper highlights how the singlet and triplet amide ligand centered ( 1,3 LC) and interligand charge transfer ( 1,3 ICT) states in (carbene)M(amide), M = Cu, Au (cMa) complexes influence the excited state properties when the triplet states are close in energy. To that end we prepared a set of five cMa complexes, in which the amide (i.e., 5 H -benzo[ b ]carbazole, H-BnCz) was kept constant giving a 3 LC energy of ca. 2.15 eV. Four different carbene ligands were selected to develop M BnCz Carbene complexes which have energies for the ICT state that vary from being either markedly higher, lower, or close to the energy of the 3 LC state on the amide ligand. Steady-state and time-resolved spectroscopic studies show that the emission spectrum of the cMa complex mirrors the phosphorescence of the parent H-BnCz amide and has a luminescence decay lifetime in the millisecond regime when the lowest energy excited state is 3 LC. When the lowest energy states are 1,3 ICT in nature, the emission band is broad and featureless, giving a lifetime in the nanosecond regime. As the 3 LC and 1,3 ICT states have comparable energies, dynamic equilibrium between the states is observed with the luminescence consisting of a mixture of 3 LC and 1,3 ICT transitions. The measured lifetime of this equilibrating system is between 45 and 350 μs depending on the solvent, for both copper- and gold-based cMa complexes. These complexes demonstrate the ability to “park” the excited state population in the 3 LC state, allowing it to act as a reservoir for thermally activated emission, while still maintaining a very rapid equilibrium between LC and ICT states.","journal":"The Journal of Physical Chemistry C","year":2025,"id":585751,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":0,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9623,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2025-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1499605,"name":"Thabassum A. Nattikallungal","orcid":"0000-0001-7077-3437","position":1,"is_corresponding":false},{"id":897227,"name":"Peter I. Djurovich","orcid":"0000-0001-6716-389X","position":2,"is_corresponding":false},{"id":1499606,"name":"Stephen E. Bradforth","orcid":"0000-0002-6164-3347","position":3,"is_corresponding":false},{"id":897228,"name":"Mark E. Thompson","orcid":"0000-0002-7764-4096","position":4,"is_corresponding":false},{"id":1399203,"name":"Kelly Biv","orcid":"0009-0005-8587-8190","position":0,"is_corresponding":true}],"reference_count":46,"raw_metadata":null,"created_at":"2026-07-19T02:59:24.273134Z","pmid":null,"pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}