Synthesis and Photochromic Properties of Molecules Containing [e]-Annelated Dihydropyrenes. Two and Three Way π-Switches Based on the Dimethyldihydropyrene−Metacyclophanediene Valence Isomerization

• Published in: Journal of the American Chemical Society 2003-03, Vol.125 (10), p.2974-2988
• Main Authors: Mitchell, Reginald H, Ward, Timothy R, Chen, Yongsheng, Wang, Yunxia, Weerawarna, S. Ananda, Dibble, Peter W, Marsella, Michael J, Almutairi, Adah, Wang, Zhi-Qiang
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Solution properties; Solutions
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0288136

The syntheses of several new simple negative, a simple positive, and multiple negative photochromes containing the dihydropyrene−cyclophanediene photochromic system are described. The photo-openings of the negative photochromes, the [e]-annelated benzo (7), naphtho (9), anthro (11), furano (19), and triphenyleno (15) derivatives of the parent 2,7-di-tert-butyl-trans-10b,10c-dimethyl-dihydropyrene (5), as well as its 4,5-dibromo derivative (13), are described to give the corresponding cyclophanedienes, as well as their photoclosures and thermal closures back to the dihydropyrenes. These are compared to the results obtained for the positive photochrome dibenzo[e,l]dihydropyrene (21) and to the bis(dihydropyreno)chrysene (44) and the (dihydropyrenobenzo)(benzo)metacyclophanediene (47) photochromes, which have more than one photochromic switch present and thus have more than a simple “on−off” state. Thermodynamic data are obtained for the thermal closing reactions. The anthrodihydropyrene (12) has the fastest thermal closing (τ1/2 = 20 min), while the furanodihydropyrene (19‘) has the slowest (τ1/2 = 63 h) at 46 °C. An electrochemical readout of the state of the switch is demonstrated for the benzodihydropyrene (7).