Table 2. Yields and TOFs for the Photochemical Regeneration of BNAH, Gibbs Free Energy (ΔG) for Photoinduced Electron Transfer from the Sensitizers to [Cp*Rh(bpy)(H₂O)]²⁺, Excited-State Quenching Rate Constants (k_q) for Bimolecular Reactions with [Cp*Rh(bpy)(H₂O)]²⁺, and Quenching Efficiencies (η) at a Given [Cp*Rh(bpy)(H₂O)]²⁺ Concentration.

	yield/%	TOF/h–1	ΔGET,1a/eV	kqb/108 M–1s–1	η([Cp*Rh(bpy)(H2O)]2+)c/%	ΔGET,2d/eV	η(TEOA)e/%	initial TONf (PS)
[Ru(bpy)3]2+	13	16	–0.07	1.2	0.77	–0.53	n/d	26
[Ir(sppy)3]3–	46	80	–1.15	41.7	40.4	0.00	n/d	92
[Ir(Fsppy)3]3–	56	111	–1.11	41.2	47.1	–0.15	n/d	113
[Ir(dFsppy)3]3–	64	146	–1.02	41.3	46.6	–0.29	6.3	128

^aGibbs free energies (ΔG) were calculated based on ΔG = −e × (E_red⁰ – E_ox*), where e is the elementary charge, E_ox* is the excited state oxidation potential of the used sensitizers (Table 1, column 4), and E_red⁰ is the ground-state reduction potential of the Rh catalyst (−0.74 V vs SCE).⁷²

^bDetermined by time-resolved luminescence spectroscopy using the TCSPC technique with solutions containing individual photosensitizers (50 μM) and [Cp*Rh(bpy)Cl]Cl (0 to 500 μM) in deaerated Tris-buffer (0.1 M, pH 8.8) at 20 °C.

^cThe quenching efficiency η was estimated based on η = (τ₀ – τ)/τ₀ = (k_q × [Q])/(τ₀^–1 + k_q × [Q]), where k_q is the reaction rate constant, τ₀ is the natural excited-state lifetime of the sensitizers (Table 1, column 5), and [Q] is the concentration of the [Cp*Rh(bpy)(H₂O)]²⁺ quencher under reaction conditions (0.1 mM).

^dGibbs free energies (ΔG) were calculated based on ΔG = −e × (E_red⁰ – E_ox⁰), where e is the elementary charge, E_ox⁰ is the oxidation potential of TEOA, and E_red⁰ is the acceptor reduction potential (Table 1, column 3). For the calculation of ΔG_ET,2, an oxidation potential of 0.76 V versus SCE was used for TEOA.⁶⁵

^eThe quenching efficiency η was determined based on η = (τ₀ – τ)/τ_0, where τ₀ is the natural excited-state lifetime (Table 1), and τ is the lifetime measured in the presence of 1 M TEOA (Figure S6).

^fFor details, see Supporting Information Section 3.