Proof for the concerted inversion mechanism in the trans→ cis Isomerization of azobenzene using hydrogen bonding to induce isomer locking

H. M.Dhammika Bandara, Tracey R. Friss, Miriam M. Enriquez, William Isley, Christopher Incarvito, Harry A. Frank, Jose Gascon, Shawn C. Burdette

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(Figure Presented) Azobenzene undergoes reversible cis-trans photoisomerization upon irradiation. Substituents often change the isomerization behavior of azobenzene, but not always in a predictive manner. The synthesis and properties of three azobenzene derivatives, AzoAMP-1, -2, and -3, are reported. AzoAMP-1 (2,2′-bis[N-(2-pyridyl)methyl]diaminoazobenzene), which possesses two aminomethylpyridine groups ortho to the azo group, exhibits minimal trans→cis photoisomerization and extremely rapid cis→trans thermal recovery. AzoAMP-1 adopts a planar conformation in the solid state and is much more emissive (φfl = 0.003) than azobenzene when frozen in a matrix of 1:1 diethylether/ethanol at 77 K. Two strong intramolecular hydrogen bonds between anilino protons and pyridyl and azo nitrogen atoms are responsible for these unusual properties. Computational data predict AzoAMP-1 should not isomerize following S2←S0 excitation because of the presence of an energy barrier in the S1 state. When potential energy curves are recalculated with methyl groups in place of anilino protons, the barrier to isomerization disappears. The dimethylated analogue AzoAMP-2 was independently synthesized, and the photoisomerization predicted by calculations was confirmed experimentally. AzoAMP-2, when irradiated at 460 nm, photoisomerizes with a quantum yield of 0.19 and has a much slower rate of thermal isomerization back to the trans form compared to that of AzoAMP-1. Its emission intensity at 77 K is comparable to that of azobenzene. Confirmation that the AzoAMP-1 and -2 retain excited state photochemistry analogous to azobenzene was provided by ultrafast transient absorption spectroscopy of both compounds in the visible spectral region. The isomerization of azobenzene occurs via a concerted inversion mechanism where both aryl rings must adopt a collinear arrangement prior to inversion. The hydrogen bonding in AzoAMP-1 prevents both aryl rings from adopting this conformation. To further probe the mechanism of isomerization, AzoAMP-3, which has only one anilinomethylpyridine substituent for hydrogen bonding, was prepared and characterized. AzoAMP-3 does not isomerize and exhibits emission (φfl = 0.0008) at 77 K. The hydrogen bonding motif in AzoAMP-1 and AzoAMP-3 provides the first example where inhibiting the concerted inversion pathway in an azobenzene prevents isomerization. These molecules provide important supporting evidence for the spectroscopic and computational studies aimed at elucidating the isomerization mechanism in azobenzene.

Original languageEnglish (US)
Pages (from-to)4817-4827
Number of pages11
JournalJournal of Organic Chemistry
Issue number14
StatePublished - Jul 16 2010


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