Aqueous photo-RAFT polymerizations catalyzed by ZnPcS₄⁻ under NIR light^a.

#	RAFT agent	PC	Deoxygenation	Reducing agent	Time (hour)	α (%)	k p app (hour−1)	M n,theo b (g mol−1)	M n,GPC c (g mol−1)	Đ c
1	CTCPA	ZnPcS4−	Yes	—	10	9	0.01	2100	2600	1.16
2	CTCPA	ZnPcS4−	Yes	TEOA	3	20	0.08	4300	4900	1.12
3	CTCPA	—	Yes	—	10	0	—	—	—	—
4	CTCPA	—	Yes	TEOA	10	0	—	—	—	—
5	CTCPA	ZnPcS4−	No	—	0	0	—	—	—	—
6	CTCPA	ZnPcS4−	No	TEOA	3	65	0.36	13 200	13 000	1.09
7	CTCPA	—	No	TEOA	10	0	—	—	—	—
8d	CTCPA	ZnPcS4−	No	TEOA	10	0	—	—	—	—
9	—	ZnPcS4−	No	TEOA	10	18	—	—	260 700	2.62
10	—	ZnPcS4−	Yes	TEOA	10	0	—	—	—	—

^aNotes: Reactions were performed at room temperature under NIR light (λ_max = 730 nm; I = 60 mW cm⁻²) in water at [DMA]/[water] = 50 (v/v). A fixed reaction stoichiometry of [DMA] : [CTCPA] : [TEOA] : [ZnPcS₄⁻] = 200 : 1 : 4 : 0.01 (50 ppm ZnPcS₄⁻ relative to monomer) was used.

^bTheoretical molecular weight was calculated using the following equation: M_n,theo = [M]₀/[RAFT agent]₀ × MW^M × α + MW^{RAFT agent}, where [M]₀, [RAFT agent]₀, MW^M, α, and MW^{RAFT agent} correspond to initial monomer concentration, initial RAFT agent concentration, molar mass of monomer, monomer conversion determined by ¹H NMR, and molar mass of RAFT agent, respectively.

^cMolecular weight and dispersity (Đ) were determined by GPC analysis (DMAC as eluent) calibrated using PMMA standards.

^dReaction was placed in the dark.