A-Frame-Containing Organometallic Oligomers ...

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Title A-Frame-Containing Organometallic Oligomers Constructed From Homo- and Heterobimetallic M(μ-dppm)2M′ (M/M′ = Pd, Pt) Building Blocks
Author(s) Sebastien Clement, Shawkat M. Aly, Jerome Husson, Daniel Fortin, Carsten Strohmann, Michael Knorr, Laurent Guyard, Alaa S. Abd-El-Aziz, Pierre D. Harvey
Journal European Journal of Inorganic Chemistry,
Date 2009
Volume 2009
Issue 17
Start page 2536
End page 2546
Abstract The homo- and heterodinuclear complexes XM(μ-dppm)2M′X (M = M′ = Pd, X = Cl 1a; M = M′ = Pd, X = I 1b; M = Pd, M′ = Pt, X = Cl 2a; M = Pd, M′ = Pt, X = I 2b; M = M′ = Pt, X = Cl 3a; M = M′ = Pt, X = I 3b) react with the diisocyanide ligand 1,2-bis(2-isocyanophenoxy)ethane (diNC) or the more soluble 1,2-bis(2-isocyano-4-tert-butylphenoxy)ethane (tBudiNC) in a 1:1 ratio to provide the thermally stable polymeric materials 4–9 {[XM(μ-dppm)2M′(μ-CN-C6H3R-2-OCH2CH2O-2-C6H3R-NC)]X}n (M = M′ = Pd, R = H, X = Cl 4a, I 4b; R = tBu, X = Cl 7; M = M′ = Pt, R = H, X = Cl 5a, I 5b; R = tBu, X = Cl 8; M = Pd, M′ = Pt, R = H, X = Cl 6a, I 6b; R = tBu, X = Cl 9). These A-frame-containing materials have been characterized in solution or in the solid state by 31P NMR (MAS) spectroscopy, elemental analysis, MALDI-TOF, DSC, TGA, IR and T1/NOE [31P NMR spin-lattice relaxation time and nuclear Overhauser enhancement constant (NOE) measurements]. The IR, Raman [ν(CN) bridging vs. terminal] and NMR spectroscopic data reveal the presence of an A-frame structure for these new materials. Evidence of an oligomer (including at least two units, determined by T1/NOE experiments) – polymer equilibrium in solution was obtained at room temperature. These polymers are luminescent (phosphorescence) at 77 K in solution and in the solid state, exhibiting broad emission bands in the 500–800 nm range.
DOI 10.1002/ejic.200900103

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