Summary We introduce techniques for probing the dynamics of triplet states. We employ these tools, along with conventional techniques, to develop a detailed understanding of a complex chemical system: a negative-tone, radical photoresist for multiphoton absorption polymerization in which isopropylthioxanthone (ITX) is the photoinitiator. This work reveals that the same color of light used for the 2-photon excitation of ITX, leading to population of the triplet manifold through intersystem crossing, also depletes this triplet population via linear absorption followed by reverse intersystem crossing (RISC). Using spectroscopic tools and kinetic modeling, we identify the reactive triplet state and a non-reactive reservoir triplet state. We present compelling evidence that the deactivation channel involves RISC from an excited triplet state to a highly vibrationally excited level of the electronic ground state. The work described here offers the enticing possibility of understanding, and ultimately controlling, the photochemistry and photophysics of a broad range of triplet processes.

A templated synthetic approach to porous organic polymers, in which branched, rigid monomers are pre-assembled around a target ion before polymerization, can significantly enhance the ion adsorption capacity of the resulting polymer.

Two sulfonate ester derivatives of anthraquinone, 1-tosyloxy-2-methoxy-9,10-anthraquinone (1a) and 1-trifluoromethylsulfonoxy-2-methoxy-9,10-anthraquinone (1b) were prepared and their ability to produce strong acids upon photoexcitation was examined. It is shown that these compounds generate acid with a yield that increases with light intensity when the applied photon dose is held constant. Additional experiments show that the rate of acid generation increases 4 fold when visible light (532 nm) laser pulses are combined with ultraviolet (355 nm) compared with ultraviolet alone.Continuous wave diode laser photolysis also effects acid generation with a rate that depends quadratically on the light intensity. Density functional theory calculations, laser flash photolysis, and chemical trapping experiments support a mechanism whereby an initially formed triplet state (T 1 ) is excited to a higher triplet state which in turn undergoes homolysis of the RS(O 2 )-OAr bond. Secondary reactions of the initially formed sulfonyl radicals produce strong acids. It is demonstrated that high intensity photolysis of either 1a or 1b can initiate cationic polymerization of ethyl vinyl ether.

The behavior of the N,N-di(4-bromophenyl)nitrenium ion under acidic aqueous conditions was examined via laser flash photolysis experiments. A long-lived species forms and can be assigned as the cation radical or the dication. This species is unreactive towards nucleophiles and reactive towards strong electron donors, consistent with a cation radical. Mechanistic analysis indicates its formation is through a separate pathway than that of the nitrenium ion, suggestive of a triplet mechanism.

A visible light absorbing, anthraquinone derivative 1-tosyloxy-2-methoxy-9,10-anthraquinone (QT) mediates both cationic and radical polymerizations depending on the intensity of visible light used. A previous study showed that this initiator generates para-toluenesulfonic acid through a stepwise, two-photon excitation mechanism. Thus, under high intensity irradiation, QT generates acid in sufficient quantities to catalyze the cationic ring opening polymerization of lactones. However, under low intensity (lamp) conditions, the two-photon process is negligible, and QT photooxidizes DMSO, generating methyl radicals which initiate the RAFT polymerization of acrylates. This dual capability was utilized to switch between radical and cationic polymerizations to synthesize a copolymer using a one-pot procedure.