Multiphoton Control of 6π Photocyclization via State-Dependent Reactant-Product Correlations.

Multiphoton excitation promises opportunities for opening new photochemical reaction pathways and controlling photoproduct distributions. We demonstrate photonic control of the 6π photocyclization of -terphenyl to make 4,4-dihydrotriphenylene (DHT). Using pump-repump-probe spectroscopy we show that 1 + 1' excitation to a high-lying reactant electronic state generates a metastable species characterized by a red absorption feature that accompanies a repump-induced depletion in the one-photon -dihydro product (-DHT); signatures of the new photoproduct are clearer for a structural analogue of the reactant that is sterically inhibited against one-photon cyclization.

Two-electron transfer stabilized by excited-state aromatization.

The scientific significance of excited-state aromaticity concerns with the elucidation of processes and properties in the excited states. Here, we focus on TMTQ, an oligomer composed of a central 1,6-methano[10]annulene and 5-dicyanomethyl-thiophene peripheries (acceptor-donor-acceptor system), and investigate a two-electron transfer process dominantly stabilized by an aromatization in the low-energy lying excited state. Our spectroscopic measurements quantitatively observe the shift of two π-electrons between donor and acceptors.

Structural Control of Nonadiabatic Photochemical Bond Formation: Photocyclization in Structurally Modified ortho-Terphenyls.

Understanding how molecular structure impacts the shapes of potential energy surfaces and prospects for nonadiabatic photochemical dynamics is critical for predicting and controlling the chemistry of molecular excited states. Ultrafast transient absorption spectroscopy was used to interrogate photoinduced, nonadiabatic 6π cyclization of a collection of ortho-terphenyls (OTP) modified with alkyl substituents of different sizes and electron-donating/withdrawing character positioned on its central and pendant phenyl rings. OTP alkylated at the 4,4″ and 4',5' positions of the pendant and central rings, respectively, exhibiting biphasic excited-state relaxation; this is qualitatively similar to relaxation of OTP itself, including a fast decrease in excited-state absorption (τ1 = 1-4 ps) followed by formation of metastable cyclized photoproducts (τ2 = 3-47 ps) that share common characteristic spectroscopic features for all substitutions despite variations in chemical nature of the substituents.

Curtin-Hammett and steric effects in HOBt acylation regiochemistry.

While hydroxybenzotriazole is commonly used in a variety of bond-forming reactions, its acylation has been shown to produce a regiochemical (O vs N) mixture with complex kinetic behavior. Increased steric bulk on the electrophile favors formation of the oxygen-acylated product. Upon standing as a solid, the mixture can isomerize completely to the nitrogen adduct.