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

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. The (R,R)‐ and (S,S)‐bis(o‐anisylphenylphosphanyl)methane and bis(m‐xylylphosphanyl)methane ligands (dppm*) react with Cu(BF4)2/Cu and Ag(BF4) to form the chiral binuclear complexes, which in turn react with 1,8‐diisocyano‐p‐menthane (dmb) to give the first P‐stereogenic 1D coordination polymers {[M2(dppm*)2(dmb)2](BF4)2}n. The isostrutural nature of these new polymers with the parent symmetric dppm‐containing polymers was unambiguously demonstrated by using a combination of several structure elucidation methods. All compounds and polymers were also characterized by circular dichroism spectroscopy.