Table 1. Photophysical and electrochemical data for the photoredox catalysts.

	λabs a (MLCT) (nm; log ε)	PLQY b	MLCT c (%)	ΔE T d (eV)	E ox e (V vs. SCE)	E red f (V vs. SCE)	E * ox g (V vs. SCE)	E * red h (V vs. SCE)	τ obs i (μs)
Ptdfppy	380 (3.76)	0.31	28	2.73	0.62 (qr)	–2.46	–2.11	0.27	0.382 ± 0.059
Ptppy	386 (3.91)	0.44	27	2.64	0.57 (irr)	–2.38	–2.07	0.26	2.21 ± 0.14
PtOMe	420 (3.78)	0.74	15	2.45	0.52 (irr)	–2.20	–1.93	0.25	11.6 ± 0.50

^a10 μM in acetonitrile solutions, 298 K.

^bPhotoluminescence quantum yields determined relative to the fluorescein standard (0.1 N NaOH (aq), PLQY = 0.79).

^cMLCT contribution to the triplet transition estimated using AOMix based on the TD-DFT (CPCM(CH₃CN)-TD-B3LYP/LANL2DZ:6-311+G(d,p)//B3LYP/LANL2DZ:6-311+G(d,p)) results.

^dTriplet-state energy determined from the phosphorescence spectra.

^eDetermined using cyclic and differential pulse voltammetry. Conditions: scan rate = 100 and 0.4 mV s^–1 for CV and DPV, respectively; 1.0 mM Pt complex in Ar-saturated acetonitrile containing the 0.10 M Bu₄NPF₆ supporting electrolyte; a Pt wire counter electrode and a Pt microdisc working electrode; the Ag/AgNO₃ couple as the pseudo-reference electrode; qr = quasi-reversible; irr = irreversible.

^fEstimated using E _red = E _ox – ΔE _g, where ΔE _g is the optical band gap energy: Ptdfppy, 3.08 eV; Ptppy, 2.95 eV; PtOMe, 2.72 eV.

^g E * ox = E _ox – ΔE _T.

^h E * red = E _red + ΔE _T.

ⁱPhotoluminescence lifetimes observed at λ _em = 465 nm (Ptdfppy), 483 nm (Ptppy), and 543 nm (PtOMe). The measurements were collected in triplicate.