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The Synthesis, X-ray Structure Analysis, and Photoisomerization Assessment of the Acyclic Triazenes 4-[(E)-2-(biphenyl-4-yl)diazenyl]-morpholine and 1,3-Bis(biphenyl-4-yl)triazene

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Abstract

The acyclic triazenes 4-[(E)-2-(biphenyl-4-yl)diazenyl]-morpholine (1) and 1,3-bis(biphenyl-4-yl)triazene (2) were prepared and their X-ray crystal structures determined. Compound 1 crystallized in the monoclinic space group P21/c with a = 29.153 (5) Å, b = 6.0444 (14) Å, c = 7.5997 (15) Å, and β = 96.03 (1)°. Compound 2 crystallized as the 1/4 cyclohexane solvate in the triclinic space group P \(\bar{1}\) with a = 10.3228 (10) Å, b = 13.4541 (14) Å, c = 15.4323 (15) Å, α = 87.158 (4)°, β = 76.030 (4)° and γ = 71.492 (5)°. The N–N double bond in 1 and 2 adopted an (E)-configuration and had bond angles that ranged from 112.19 (9)° to 114.01 (13)°, which deviated from optimal trigonal planar geometry by 6°–8°. A degree of π-conjugation across the acyclic triazene moieties in compounds 1 and 2 was indicated by N–N double and single bond lengths that were respectively longer and shorter than the literature values for these types of bonds. The room temperature electronic absorption spectra of 1 and 2 in various solvents were both dominated by an intense band above 300 nm that was assigned to a combination of π → π* and n → π* transitions. Compounds 1 and 2 in acetonitrile and methanol solution were found to undergo trans → cis photoisomerization. The magnitudes of trans → cis rate constants were rationalized in terms of the degree of solvent stabilization of the dipolar resonance hybrid structure of the acyclic triazene subunits in 1 and 2. Irradiation of chloroform solutions of 1 and 2 caused trans → cis photoisomerization and radical decomposition to occur.

Graphical Abstract

The X-ray structures of compounds 1 and 2 were determined and their photoisomerization kinetics explored.

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Scheme 1
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Scheme 2

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Acknowledgments

Whittier College is acknowledged for support of this research. The upgrade of the diffractometer was made possible by Grant No. LEQSF (2011–2012)-ENH-TR-01, which was administered by the Louisiana Board of Regents. Dr. Simon Jones is thanked for providing HR–ESI–MS of compounds 1 and 2.

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Authors and Affiliations

  1. Department of Chemistry, Whittier College, 13406 Philadelphia Street, Whittier, CA, 90608, USA

    Carolyn Mukai, Emanuel Zamora, Jillian L. Blatti & Ralph Isovitsch

  2. Department of Chemistry, Louisiana State University, Baton Rouge, LA, 70803, USA

    Frank R. Fronczek

Authors
  1. Carolyn Mukai
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  2. Emanuel Zamora
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  3. Jillian L. Blatti
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  4. Frank R. Fronczek
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  5. Ralph Isovitsch
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Corresponding author

Correspondence to Ralph Isovitsch.

Electronic Supplementary Material

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Fig. S1

Irradiation device used in photoisomerization experiments. Commercially available black lights are ~6 cm to the left and right of the sample (DOC 3634 kb)

Fig. S2

Electronic absorption spectra of the irradiation of a dilute CH3CN solution of compound 1 taken at 1-min intervals from 0 to 25 min. Isosbestic points were observed at 235 and 274 nm (DOC 268 kb)

Fig. S3

Electronic absorption spectra of the irradiation of a dilute CH3CN solution of compound 2 taken at 1-min intervals from 0 to 20 min. Isosbestic points were observed at 235 and 305 nm (DOC 364 kb)

Fig. S4

Electronic absorption spectra of the irradiation of a dilute CHCl3 solution of compound 1 taken at 0, 0.5 and 1.5 min (DOC 128 kb)

Fig. S5

Electronic absorption spectra of the irradiation of a dilution CHCl3 solution of compound 2 taken at 1-min intervals from 0 to 15 min. An isosbestic point was observed at 296 nm (DOC 313 kb)

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Mukai, C., Zamora, E., Blatti, J.L. et al. The Synthesis, X-ray Structure Analysis, and Photoisomerization Assessment of the Acyclic Triazenes 4-[(E)-2-(biphenyl-4-yl)diazenyl]-morpholine and 1,3-Bis(biphenyl-4-yl)triazene. J Chem Crystallogr 43, 412–420 (2013). https://doi.org/10.1007/s10870-013-0438-6

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  • DOI: https://doi.org/10.1007/s10870-013-0438-6

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