Nanocluster-Containing Mesoporous Magnetoceramics from Hyperbranched Organometallic Polymer Precursors

Pyrolysis of hyperbranched poly[1,1‘-ferrocenylene(methyl)silyne] (5) yields mesoporous, conductive, and magnetic ceramics (6). Sintering at high temperatures (1000−1200 °C) under nitrogen and argon converts 5 to 6N and 6A, respectively, in ∼48−62% yields. The ceramization yields of 5 are higher than that (∼36%) of its linear counterpart poly[1,1‘-ferrocenylene(dimethyl)silylene] (1), revealing that the hyperbranched polymer is superior to the linear one as a ceramic precursor. The ceramic products 6 are characterized by SEM, XPS, EDX, XRD, and SQUID. It is found that the ceramics are electrically conductive and possess a mesoporous architecture constructed of tortuously interconnected nanoclusters. The iron contents of 6 estimated by EDX are 36−43%, much higher than that (11%) of the ceramic 2 prepared from the linear precursor 1. The nanocrystals in 6N are mainly α-Fe2O3 whereas those in 6A are mainly Fe3Si. When magnetized by an external field at room temperature, 6A exhibits a high-saturation magnetization (Ms ∼ 49 emu/g) and near-zero remanence and coercivity; that is, 6A is an excellent soft ferromagnetic material with an extremely low hysteresis loss.