Fluorescence in Rhoda- and Iridacyclopentadienes Neglecting the Spin–Orbit Coupling of the Heavy Atom: The Ligand Dominates

• Published in: Inorganic chemistry 2014-07, Vol.53 (13), p.7055-7069
• Main Authors: Steffen, Andreas, Costuas, Karine, Boucekkine, Abdou, Thibault, Marie-Hélène, Beeby, Andrew, Batsanov, Andrei S, Charaf-Eddin, Azzam, Jacquemin, Denis, Halet, Jean-François, Marder, Todd B
• Format: Article
• Language: English
• Subjects: Chemical Sciences
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic501115k

We present a detailed photophysical study and theoretical analysis of 2,5-bis(arylethynyl)rhodacyclopenta-2,4-dienes (1a–c and 2a–c) and a 2,5-bis(arylethynyl)iridacyclopenta-2,4-diene (3). Despite the presence of heavy atoms, these systems display unusually intense fluorescence from the S1 excited state and no phosphorescence from T1. The S1 → T1 intersystem crossing (ISC) is remarkably slow with a rate constant of 108 s–1 (i.e., on the nanosecond time scale). Traditionally, for organometallic systems bearing 4d or 5d metals, ISC is 2–3 orders of magnitude faster. Emission lifetime measurements suggest that the title compounds undergo S1 → T1 interconversion mainly via a thermally activated ISC channel above 233 K. The associated experimental activation energy is found to be ΔH ISC ⧧ = 28 kJ mol–1 (2340 cm–1) for 1a, which is supported by density functional theory (DFT) and time-dependent DFT calculations [ΔH ISC ⧧(calc.) = 11 kJ mol–1 (920 cm–1) for 1a-H]. However, below 233 K a second, temperature-independent ISC process via spin–orbit coupling occurs. The calculated lifetime for this S1 → T1 ISC process is 1.1 s, indicating that although this is the main path for triplet state formation upon photoexcitation in common organometallic luminophores, it plays a minor role in our Rh compounds. Thus, the organic π-chromophore ligand seems to neglect the presence of the heavy rhodium or iridium atom, winning control over the excited-state photophysical behavior. This is attributed to a large energy separation of the ligand-centered highest occupied molecular orbital (HOMO) and lowest unoccupied MO (LUMO) from the metal-centered orbitals. The lowest excited states S1 and T1 arise exclusively from a HOMO-to-LUMO transition. The weak metal participation and the cumulenic distortion of the T1 state associated with a large S1–T1 energy separation favor an “organic-like” photophysical behavior.