Studies on Cage‐Type Tetranuclear Metal Clusters with Ferrocenylphosphonate Ligands

Reaction of FcCH 2 PO 3 H 2 [Fc=(η 5 ‐C 5 H 5 )Fe(η 5 ‐C 5 H 4 )] (H 2 FMPA) and 1,10‐phenanthroline (phen) with Cd(OAc) 2 ⋅2 H 2 O or ZnSO 4 ⋅7 H 2 O in methanol in the presence of triethylamine resulted in the formation of two new ferrocenylphosphonate metal‐cage complexes [M 4 (fmpa) 4 (phen) 4 ]⋅ 7 CH 3 OH (M=Cd 1 , M=Zn 2 ). Both structures contain two kinds of isomeric tetranuclear metal phosphonate cages, which are linked to one another by π–π interactions between the phen molecules. In 1 , the Cd1, Cd3, and Cd4 atoms are all pentacoordinate, while the Cd2 atom is coordinated by four oxygen atoms from three phosphonate ligands and two nitrogen atoms from the chelating phen in a distorted octahedral geometry. Four Cd atoms from each unit are interconnected through bridging phosphonate ligands with different coordination modes, such as 5.221, 4.211, and 2.11 (Harris notation), yielding a {Cd 4 } cage. In 2 , each Zn atom is coordinated by three oxygen atoms from three phosphonate ligands and two nitrogen atoms from phen, leading to a distorted square‐pyramidal geometry. The four Zn atoms of each isomeric unit are also interconnected through four bridging phosphonate ligands to yield a {Zn 4 } cage. Fluorescent studies indicate that ligand‐to‐ligand charge‐transfer photoluminescence is observed for 1 , while the emisson bands of 2 can be assigned to an admixture of ligand‐to‐ligand and metal‐to‐ligand charge transfer. Solution‐state differential pulse voltammetry indicates that the half‐wave potentials of the ferrocenyl moieties in 1 and 2 have different deviations relative to the relevant H 2 FMPA ligand. This may be because the highest occupied molecular orbital (HOMO) in 1 is located in the FMPA 2− groups, while in 2 the HOMO is located in the phen and Zn II groups, so the Fe II centers in complex 1 are more easily oxidized to Fe III centers than those of 2 . The third‐order nonlinear optical (NLO) measurements show that both 1 and 2 exhibit strong third‐order NLO self‐focusing effects; hence, they are promising candidates for NLO materials. By calculating the component of the lowest unoccupied molecular orbitals of 1 and 2 , we confirmed that the co‐planar phen rings control their optical nonlinearity, while the H 2 FMPA ligands and metal ions have only a weak influence on their NLO properties.