Ultrafast Electron Dynamics of a Ferrocene-Based Butadiyne-Bridged Complex.

Kasun C Mendis, Jesús Valdiviezo, Susannah D Cox, Peng Zhang, Xiao Li, Tong Ren, David N Beratan, Igor V Rubtsov

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Article in The journal of physical chemistry. A, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.

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8 authors.

Kasun C MendisDepartment of Chemistry, Tulane University, New Orleans, Louisiana 70118, United States.

Jesús ValdiviezoDepartment of Chemistry, Duke University, Durham, North Carolina 27708, United States.ORCID 0000-0002-8542-1247

Susannah D CoxDepartment of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.

Peng ZhangDepartment of Chemistry, Duke University, Durham, North Carolina 27708, United States.

Xiao LiDepartment of Chemistry, Tulane University, New Orleans, Louisiana 70118, United States.

Tong RenDepartment of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.ORCID 0000-0002-1148-0746

David N BeratanDepartment of Chemistry, Duke University, Durham, North Carolina 27708, United States.ORCID 0000-0003-4758-8676

Igor V RubtsovDepartment of Chemistry, Tulane University, New Orleans, Louisiana 70118, United States.ORCID 0000-0002-3010-6207

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6 · The paper itself

Abstract

Photoinduced electron transfer (ET) in alkyne-linked donor-bridge-acceptor (DBA) compounds is strongly influenced by torsional flexibility, allowing control over ET without altering the donor-acceptor distance. Here, we investigate excited-state dynamics in Fc-C4-NAP, a DBA compound featuring a ferrocene (Fc) donor, a butadiyne bridge (C4), and a 1,8-naphthalimide (NAP) acceptor. Unlike analogues DBA compounds with fully organic planar donors, Fc-C4-NAP exhibits a complex excited-state manifold. Femtosecond transient absorption (TA) measurements in the visible and mid-IR regions found three characteristic relaxation times (0.3-0.5 ps, ∼2.6 ps, and 17-20 ps) following its excitation at 402 nm, which prepares NAP-centered excited states.TD-DFT computations indicate that the acceptor-based locally excited (LE) and the charge separated (CS) diabatic states are well coupled to the Fc states associated with d-states of Fe. This bridge-mediated coupling, estimated at 200-500 cm

Identifiers

PMID41838851

DOI10.1021/acs.jpca.5c08653

PMCPMC13034416

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