The Beauty and Complexity of the Mixed-Ligand Pd(II)-containing Monomers, Oligomers and Polymers Built upon Diphosphines and 1,8-Diisocyano-p-menthane

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

“…[11] Interestingly, this latter work [11] clearly demonstrated from X-ray crystallographic studies that the most common oligomer is the dimer. Attempts to estimate the M n values by MALDI-TOF spectrometry proved inconclusive since only the fragments M(µ-dppm) 2 MЈ and XM(µ-dppm) 2 MЈ (X = Cl, I, M = Pd, Pt and MЈ = Pd, Pt) were observed (see the Supporting Information for a typical example).…”

“…This result indicates the fragility of this kind of polymer under MALDI-TOF conditions. [11] Consequently, the M n values in solution were estimated by the T 1 /NOE method, which is fully explained elsewhere. [12] Only a brief description is provided here.…”

The Spectroscopy and Photophysical Behavior of Diphosphine- and Diisocyanide-Containing Coordination and Organometallic Oligomers and Polymers: Focus on Palladium and Platinum, Copper, Silver, and Gold

“…Palladium(II)-and platinum(II)-containing oligomers and polymers built with diphosphine and diisocyanide assembling ligands-which allow for the presence of metal in the backbone-are not luminescent based on the author's personal experience (e.g., 1 and 2) [12], but also according to literature (e.g., polymers 3-5) [13,14]. This contrasts drastically with the well-known palladium(II)-and platinum(II)-containing oligomers and polymers built with ethynyl assembling fragments (also called polyynes), with the general formula as shown for polymer 6 [15,16].…”

“…In solution, the polymer becomes a binuclear complex as is demonstrated by the estimation of the molecular dimension from the measurements of spin-lattice relaxation time (T 1 ) and nuclear Overhauser enhancement (NOE) constants using closely related binuclear palladium complexes. The technique was recently established [20,21], and used successfully on several occasions thereafter [12,22,23]. The driving force for such phenomena is the the ease of dissolving small molecules-with better solute-solvent interactions-rather than large polymers, particularly when the polymers do not incorporate soluble side-chains.…”

An Original Calix[4]arene‐Containing Oligomer/Polymer Catalyst for Homogeneous Hydroformylation

“…[9] In addition, organometallic and coordination polymers are known to be in equilibrium in solution between dimers, oligomers, and polymers, with often one species being dominant. [10][11][12] This group has anchored Rhcontaining fragments at diphosphinated calix [4]arene macrocycles at the upper-rim, but these amorphous materials that appear as polymers in the solid state, are essentially dimers in solution that exhibit obvious ring stress and steric hindrance (see compounds 1-8 in Scheme 1). [13] The equilibrium between the polymer (solid state) and the 'stressed' dimer (solution) is not unprecedented ({Pd 2 (dmb) 2 Cl 2 } n (solid) versus Pd 2 (dmb) 2 Cl 2 (solution); dmb ¼ 1,8-diisocyano-p-menthane).…”