NDLI: Cyclopalladated complexes of perylene imine: mononuclear complexes with five- or six-membered metallacycles

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Lentijo, Sergio Miguel, Jesús A. Espinet, Pablo
Description	Author Affiliation: Lentijo S ( IU CINQUIMA Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47071, Valladolid, Spain.)
Abstract	Mononuclear palladium complexes $[Pd(C⁁N)L_{2}]$ (HC⁁N = $3-C_{20}H_{11}CH=NC_{6}H_{4}-p-C_{2}H_{5})$ have been prepared with Pd bound to the peri site or to the ortho site of the perylenyl fragment. These metallations correspond, respectively to six-membered $(L_{2}$ = $S_{2}COMe$ (3); acac (4); Cl, $PMe_{3}$ (5); Cl, $PPh_{3}$ (6); $S_{2}CNEt_{2}$ (7)) or five-membered $(L_{2}$ = $S_{2}COMe$ (8); acac (9)) isomeric palladacyclic compounds. The X-ray structures of 3, 5, 7 and 8 show that the perylenyl fragment remains essentially flat for 3, 7 and 8 and twisted for 5. Intermolecular π–π stacking of perylenyl rings is observed only for 7. All palladium complexes exhibit fluorescence associated to the perylene fragments, with emission quantum yields (in solution at room temperature) in the range 0.01–0.12 (compared to 0.13 for the free imine ), and emission lifetimes ∼ 1 ns. The complexes with five-membered palladacycles show lower quantum yields than their six-membered analogs. The similarity in shape of the luminescence spectra of these metallated complexes with perylene , although red-shifted, strongly suggests a perylene-dominated intraligand π–π* emissive state, metal-perturbed by interaction of the perylene orbitals with the palladium fragment.
ISSN	14779226
Issue Number	29
Journal	Dalton Trans.
Volume Number	40
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2011-08-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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