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RESEARCH PRODUCT

The First P ‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

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The enantiomeric ligands (R,R)- and (S,S)-bis(o-anisylphenylphosphanyl)methane (R,R-22 and S,S-22) and (R,R)- and (S,S)-bis(phenyl-m-xylylphosphanyl)methane (R,R-23 and S,S-23; dppm*), were treated with [Cu(NCCH3)4](BF4) and AgBF4 to produce the binuclear complexes [Cu2(dppm*)2(NCCH3)4](BF4)2 or [Ag2(dppm*)2](BF4)2, respectively. Then, these complexes were used as building blocks to prepare the first P-chirogenic 1D coordination polymers {[M2(dppm*)2(dmb)2](BF4)2}n [dppm* = (R,R)-22, (S,S)-22, (R,R)-23, (S,S)-23, M = Cu, Ag, dmb = 1,8-diisocyano-p-menthane] where M is part of the backbone of the polymer chain. The isostructural nature of these new polymers with the achiral parent polymers, {[M2(dppm)2(dmb)2](BF4)2}n (M = Cu, Ag), was unambiguously demonstrated with a combination of methods including 1H NMR, chemical analysis, UV/Vis spectrometry, emission spectroscopy and emission lifetime measurements. The structure of the bimetallic complex [Ag2(R,R-23)2](BF4)2 was solved by X-ray crystallography, and all enantiomeric complexes and polymers were characterized by circular dichroism spectroscopy.