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In solutions, 2\u03c0+2\u03c0 photodimers of N\u2010cyano and N\u2010acyl dibenzazepines are formed via the triplet state upon acetone\u2010 or benzophenone\u2010sensitized energy transfer. T\u2013T absorption spectra were measured and absorption coefficients were determined. The triplet energy transfer is equally efficient for N\u2010alkyl dibenzazepines, which do not dimerize. Excited states of n\u03c0* character in the latter cases are discussed to rationalize the different reactivities. In spite of negligible intersystem crossing of 21 dibenzazepine derivatives, photodimers of N\u2010acyl and N\u2010cyano dibenzazepines are formed upon direct excitation in concentrated solutions (0.01\u20130.1 mol\u2009dm<jats:sup>\u22123<\/jats:sup>) as well as in the solid state. A selective <jats:italic>anti<\/jats:italic>\u2010configuration of the photodimers was found throughout.<\/jats:p>","DOI":"10.1002\/chem.200305199","type":"journal-article","created":{"date-parts":[[2003,12,19]],"date-time":"2003-12-19T15:00:38Z","timestamp":1071846038000},"page":"283-293","source":"Crossref","is-referenced-by-count":10,"title":["Substituent\u2010Dependent Reactivity in the Photodimerization of N\u2010Substituted Dibenz[<i>b<\/i>,<i>f<\/i>]azepines"],"prefix":"10.1002","volume":"10","author":[{"given":"Jens","family":"Querner","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Thomas","family":"Wolff","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Helmut","family":"G\u00f6rner","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2003,12,19]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39730000244"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr60287a006"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470133439.ch3"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00041a035"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1010-6030(02)00034-5"},{"key":"e_1_2_7_6_2","volume-title":"Pharmaceutical Substances\u2014Syntheses, Patents, Applications","author":"Kleemann A.","year":"1999"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1111\/j.2042-7158.1984.tb04890.x"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/p19740000052"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270183004886"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108270186094349"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/0047-2670(87)87027-2"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.555770"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00052a025"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100053a031"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100036a037"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/1010-6030(95)04230-X"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1562\/0031-8655(2001)0730339DASPOB2.0.CO2"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20010401)7:7<1530::AID-CHEM1530>3.0.CO;2-L"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9519344"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja954340"},{"key":"e_1_2_7_21_2","first-page":"1","volume":"19","author":"G\u00f6rner H.","year":"1995","journal-title":"Adv. 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