Synthesis and characterization of bis(4-amino-2-bromo-6-methoxy)azobenzene derivatives

• Main Authors: David Martínez-López, Amirhossein Babalhavaeji, Diego Sampedro, G. Andrew Woolley
• Format: Article
• Language: English
• Published: Beilstein-Institut 2019-12-01
• Series: Beilstein Journal of Organic Chemistry
• Subjects: azobenzene; azonium; molecular switches; ortho substitution; photoisomerization; photoswitch; visible light
• Online Access: https://doi.org/10.3762/bjoc.15.296

Aminoazobenzene derivatives with four ortho substituents with respect to the N–N double bond are a relatively unexplored class of azo compounds that show promise for use as photoswitches in biology. Tetra-ortho-methoxy-substituted aminoazobenzene compounds in particular can form azonium ions under physiological conditions and exhibit red-light photoswitching. Here, we report the synthesis and characterization of two bis(4-amino-2-bromo-6-methoxy)azobenzene derivatives. These compounds form red-light-absorbing azonium ions, but only under very acidic conditions (pH < 1). While the low pKa makes the azonium form unsuitable, the neutral versions of these compounds undergo trans-to-cis photoisomerization with blue-green light and exhibit slow (τ1/2 ≈ 10 min) thermal reversion and so may find applications under physiological conditions.