TY - JOUR
T1 - Photochemistry of nitrogen-bridged cyclophanes
T2 - 2,11-Diaza[3 2]anthracenoparacyclophane and 2,11-diaza[32] paracyclophane systems
AU - Okamoto, Hideki
AU - Yamaji, Minoru
AU - Satake, Kyosuke
N1 - Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.
PY - 2008/8/1
Y1 - 2008/8/1
N2 - This account provides an overview of the photochemical properties of cyclophanes possessing nitrogen atoms in the bridge chains, namely 2,11-diaza[32]anthracenoparacyclophane and 2,11-diaza[3 2]paracyclophane systems. Although the photoreactions of aromatic molecules that are bound by a linker or fixed in a cyclophane structure have been widely investigated, much less attention has been paid to the photochemistry of aromatic rings incorporated in a nitrogen-bridged cyclophane. During the course of our work on the photoreactions of cyclophanes possessing nitrogen atoms in their bridge chains, the nitrogen-bridged cyclophanes were found to display photoproperties significantly different from those of the nonbridged aromatic chromophores or the corresponding carbonbridged cyclophane analogues. The 2,11-diaza[32]anthracenoparacyclophane system displayed an efficient photochemical cycloaddition-adiabatic cycloreversion cycle in the excited singlet state, while in the triplet state, the photoisomer underwent a novel rearrangement and adiabatic cycloreversion. Upon photolysis of the 2,11-diaza[32]paracyclophane system, an octahedrane cage was formed. This is the first reported octahedrane formation to occur by the photochemical dimerization of benzene. Thus, the title cyclophane systems display a variety of photoprocesses involving cycloaddition, adiabatic cycloreversion accompanied by photoinduced chemiluminescence, novel rearrangements, and previously unknown benzene dimerization. 1 Introduction 2 Photochemistry of the 2,11-Diaza[32]anthracenoparacyclophane System 2.1 General Comments on the Photochemical Cycloaddition and Cycloreversion of Aromatic Molecules in the Singlet State 2.2 Intramolecular Photochemical Cycloaddition and Cycloreversion of the 2,11-Diaza[32] anthracenoparacyclophane System 2.3 General Introduction to the Photochemistry of Aromatic Molecules in the Triplet State 2.4 Photoproperties of the 2,11-Diaza[32]anthracenoparacyclo-phane System in the Triplet State 3 Photochemistry of the 2,11-Diaza[32]paracyclophane System 3.1 General Remarks on the Photoreactions of Cyclophanes Containing Two Benzene Rings 3.2 Construction of the 2,11-Diaza[32]paracyclophane Skeleton 3.3 Photoreactions of the 2,11-Diaza[32]paracyclophane System 4 Summary.
AB - This account provides an overview of the photochemical properties of cyclophanes possessing nitrogen atoms in the bridge chains, namely 2,11-diaza[32]anthracenoparacyclophane and 2,11-diaza[3 2]paracyclophane systems. Although the photoreactions of aromatic molecules that are bound by a linker or fixed in a cyclophane structure have been widely investigated, much less attention has been paid to the photochemistry of aromatic rings incorporated in a nitrogen-bridged cyclophane. During the course of our work on the photoreactions of cyclophanes possessing nitrogen atoms in their bridge chains, the nitrogen-bridged cyclophanes were found to display photoproperties significantly different from those of the nonbridged aromatic chromophores or the corresponding carbonbridged cyclophane analogues. The 2,11-diaza[32]anthracenoparacyclophane system displayed an efficient photochemical cycloaddition-adiabatic cycloreversion cycle in the excited singlet state, while in the triplet state, the photoisomer underwent a novel rearrangement and adiabatic cycloreversion. Upon photolysis of the 2,11-diaza[32]paracyclophane system, an octahedrane cage was formed. This is the first reported octahedrane formation to occur by the photochemical dimerization of benzene. Thus, the title cyclophane systems display a variety of photoprocesses involving cycloaddition, adiabatic cycloreversion accompanied by photoinduced chemiluminescence, novel rearrangements, and previously unknown benzene dimerization. 1 Introduction 2 Photochemistry of the 2,11-Diaza[32]anthracenoparacyclophane System 2.1 General Comments on the Photochemical Cycloaddition and Cycloreversion of Aromatic Molecules in the Singlet State 2.2 Intramolecular Photochemical Cycloaddition and Cycloreversion of the 2,11-Diaza[32] anthracenoparacyclophane System 2.3 General Introduction to the Photochemistry of Aromatic Molecules in the Triplet State 2.4 Photoproperties of the 2,11-Diaza[32]anthracenoparacyclo-phane System in the Triplet State 3 Photochemistry of the 2,11-Diaza[32]paracyclophane System 3.1 General Remarks on the Photoreactions of Cyclophanes Containing Two Benzene Rings 3.2 Construction of the 2,11-Diaza[32]paracyclophane Skeleton 3.3 Photoreactions of the 2,11-Diaza[32]paracyclophane System 4 Summary.
KW - Chromophores
KW - Cycloadditions
KW - Cyclophanes
KW - Photochemistry
KW - Rearrangements
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U2 - 10.1055/S-2008-1078574
DO - 10.1055/S-2008-1078574
M3 - Article
AN - SCOPUS:49649103852
SP - 1931
EP - 1945
JO - Synlett
JF - Synlett
SN - 0936-5214
IS - 13
ER -