Novel Photocatalyst Based on Through‐Space Charge Transfer Induced Intersystem Crossing Enables Rapid and Efficient Polymerization Under Low‐Power Excitation Light.

Currently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through‐space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole‐naphthalimide (NI) dyad (NI‐1) characterized by long triplet excited state lifetime (τT=62 μs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=−1.93 eV, Triplet: E1/2 (PC+1/*PC)=−0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm−2) and low catalyst (NI‐1) loading (<50 μM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI‐4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 μm. [ABSTRACT FROM AUTHOR]