A‐Frame‐Containing Organometallic Oligomers Constructed From Homo‐ and Heterobimetallic M(μ‐dppm)2M′ (M/M′ = Pd, Pt) Building Blocks

• Published in: European journal of inorganic chemistry 2009, Vol.2009 (17), p.2536-2546
• Main Authors: Clément, Sébastien, Aly, Shawkat M., Husson, Jérôme, Fortin, Daniel, Strohmann, Carsten, Knorr, Michael, Guyard, Laurent, Abd‐El‐Aziz, Alaa S., Harvey, Pierre D.
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Isocyanide ligands; Luminescence; Palladium; Platinum; Polymers
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200900103

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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) The complexes XM(μ‐dppm)2M′X react with 1,2‐bis(2‐isocyanophenoxy)ethanes (diNC) in a 1:1 molar ratio to give the corresponding polymers {[{M(μ‐dppm)2M′X}(diNC)]X}n. These polymers are luminescent in solution at 77 K, showing strong luminescence bands in the range 500–800 nm with lifetimes of between 0.2 and 5.6 μs.