Divergent structural motifs from (R)-PhosH: A trinuclear Cu(II) cluster and pyridine-coordinated Co(II)/Zn(II) 1D-polymers

The coordination chemistry of the axially chiral BINOL-derived phosphate ligand ( R )-PhosH with first-row transition metals remains underexplored. Herein, we report three new Cu(II), Co(II), and Zn(II) complexes displaying metal- and coordination-environment-dependent differences in nuclearity and dimensionality. Reaction with Cu(OTf) 2 affords the discrete trinuclear cluster {Cu 3 -[P] 6 ·(H 2 O) 3 }·27H 2 O 1 ·27H 2 O ([P] = − μ-η 2 -( R )-Phos-κ 2 O:κO´), featuring interconnected eight- and twelve-membered metallacycles. In contrast, pyridine-assisted crystallization of the Co(II) and Zn(II) systems yields the chiral one-dimensional coordination polymers {[Co 2 -[P] 2 (H 2 O) 3 (Py) 5 ]·(OTf) 2 } n , 2 , and {[Zn 2 -[P] 2 (H 2 O) 2 (Py) 5 ]·(OTf) 2 } n , 3 , respectively. The Co(II) polymer contains two distorted octahedral centers, whereas the Zn(II) derivative combines octahedral and trigonal-bipyramidal sites. Magnetic measurements on 1 and 2 reveal predominantly paramagnetic behaviour at high temperature and nonlinear M(H) responses at 1.8 K. The Cu(II) cluster exhibits very weak Cu Cu exchange, with the FC and ZFC susceptibility fits statistically compatible with J HDVV = 0, whereas the Co(II) response is dominated by single-ion anisotropy and weak antiferromagnetic coupling ( J HDVV = −0.17 ± 0.05 cm −1 ). These results highlight the ( R )-PhosH ligand as a versatile platform for constructing structurally diverse chiral metal assemblies.