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2,11-dialkylated 1,12-diazaperylene copper(I) complexes : first supramolecular column assemblies by pi-pi stacking between homoleptic tetrahedral metal complexes, exhibiting low-energy MLCT transitions

  • 2,11-Dialkylated 1,12-diazaperylenes (alkyl = Me, Et, iPr) dmedap, detdap and dipdap have been synthesized by reductive cyclization of 3,3-dialkylated 1,1-biisoquinolines 3a-c, resulting in the first copper(I) complexes of a large- surface ligand. The new copper(I) complexes show low-energy MLCT absorptions unprecedented for bis(-diimin)copper(I) complexes. The solid structures of the complexes[Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, [Cu(dipdap)2]OTf·CH2Cl2, [Cu(dipdap)2]I·C2H4Cl2·THF·2H2O, [Cu(dmedap)2]OTf and [Cu(dipdap)2]AQSO3·H2O (AQSO3 = sodium 9,10-dihydro-9,10-dioxo-2- anthracenesulfonate) are reported. In [Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, each copper(I) complex cation interacts with two others by - stacking interactions forming a novel supramolecular column structural motif running along the crystallographic c axis. In the crystalline compound [Cu(dipdap)2]AQSO3·H2O, aggregation between two complex cations and two additional anions by - stacking interactions is observed, leading to a tetrameric assembly. Furthermore, the three complex2,11-Dialkylated 1,12-diazaperylenes (alkyl = Me, Et, iPr) dmedap, detdap and dipdap have been synthesized by reductive cyclization of 3,3-dialkylated 1,1-biisoquinolines 3a-c, resulting in the first copper(I) complexes of a large- surface ligand. The new copper(I) complexes show low-energy MLCT absorptions unprecedented for bis(-diimin)copper(I) complexes. The solid structures of the complexes[Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, [Cu(dipdap)2]OTf·CH2Cl2, [Cu(dipdap)2]I·C2H4Cl2·THF·2H2O, [Cu(dmedap)2]OTf and [Cu(dipdap)2]AQSO3·H2O (AQSO3 = sodium 9,10-dihydro-9,10-dioxo-2- anthracenesulfonate) are reported. In [Cu(dipdap)2]BF4·CH2Cl2·1.5H2O, each copper(I) complex cation interacts with two others by - stacking interactions forming a novel supramolecular column structural motif running along the crystallographic c axis. In the crystalline compound [Cu(dipdap)2]AQSO3·H2O, aggregation between two complex cations and two additional anions by - stacking interactions is observed, leading to a tetrameric assembly. Furthermore, the three complex compounds [Cu(L)2]BF4 (L = dmedap, detdap, dipdap) were tested for sensory applications in aqueous buffer solutions in electrochemical studies of the complex immobilized on glassy carbon electrodes.show moreshow less

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Metadaten
Author:Stefan Kammer, Alexandra Kelling, Heiko Baier, Wulfhard Mickler, Carsten DoscheGND, Knut Rurack, Andreas Kapp, Fred Lisdat, Hans-Jürgen Holdt
URL:http://www3.interscience.wiley.com/journal/27721/home
DOI:https://doi.org/10.1002/ejic.200900695
ISSN:1434-1948
Document Type:Article
Language:English
Year of first Publication:2009
Year of Completion:2009
Release Date:2017/03/25
Source:European journal of inorganic chemistry. - ISSN 1434-1948. - (2009), 31, S. 4648 - 4659
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert