Peculiar properties of homoleptic Cu complexes with dipyrromethene derivatives.
In view of preparing Cu polynuclear complexes with dipyrromethene ligands, the mononuclear complexes [Cu(II)(dipy)2] (dipyH = 5-phenyldipyrromethene) and [Cu(II)(dpdipy)2] (dpdipyH = 1,5,9-triphenyldipyrromethene) have been prepared and characterized by X-ray crystallography, mass spectrometry and EPR spectroscopy. Their peculiar redox and spectroscopic (absorption/emission) behaviours are discussed. In contrast to Cu(II) complexes of 1,1'-bidypyrrin, the reduction electrolysis of [Cu(II)(dpdipy)2] leads to decomposition products on a time scale of a few hours. Moreover in relation to this observation, [Cu(I)(dpdipy)2](-) could not be synthesized in spite of the Cu(I) core protection by the phenyl substituents in ortho position of the nitrogen atoms. Theoretical calculations provide some explanations for this instability. Interestingly [Cu(II)(dipy)2] and [Cu(II)(dpdipy)2] display weak luminescence at room temperature, attributed to a ligand centered emission.
Organic Chemistry & Photochemistry, Université libre de Bruxelles, ULB, CP 160/08, 50 Avenue F.D. Roosevelt, 1050 Brussels, Belgium. akirsch@ulb.ac.be cmouche@ulb.ac.be.
Kathleen
K
Servaty
Emilie
E
Cauët
Fabrice
F
Thomas
Javiera
J
Lambermont
Pascal
P
Gerbaux
Julien
J
De Winter
Margriet
M
Ovaere
Leen
L
Volker
Nathalie
N
Vaeck
Luc
L
Van Meervelt
Wim
W
Dehaen
Cécile
C
Moucheron
Andrée
A
Kirsch-De Mesmaeker
D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D011162:Porphobilinogen / Q000031:analogs & derivatives* / Q000737:chemistry
D056831:Coordination Complexes; C507544:dipyrromethene; D011162:Porphobilinogen; D003300:Copper