We successfully observed the phenomenon of “nonequilibrium local heating” occurring to the DMSO molecules in proximity of the Co particles under microwave irradiation by real-time in situ Raman spectroscopy. This phenomenon was induced only under microwave irradiation but not by conventional heating. This nonequilibrium local heating can be realized by the input of the power more rapid than that of the heat loss induced by the temperature difference between the heated microdomains and the surrounding domains. We have demonstrated the enhancement in the dehalogenation reaction of the C(sp3)−Cl bond of 2-chloroethylbenzene and 4-phenylbutyl chloride caused by the “nonequilibrium local heating” of the surface of the Co and/or Fe particles under microwave irradiation.

SI-1. InstrumentsUV-vis spectra were obtained using a V-570 spectrometer (JASCO CO.). 1 H NMR spectra were recorded using a Joel jnm-GSX400 (400 MHz). The measurement was taken in CDCl 3 using tetramethylsilane (TMS) as an internal standard. SI-2. Yield of Ni 50 Co 50Yield of Ni 50 Co 50 was calculated from the weight of the obtained powder. Ni 2+ (12.5 mmol) and Co 2+ (12.5 mmol) were used for the synthesis of Ni-Co nanoparticles. The composition in the obtained powder was confirmed as Ni 50 Co 50 from the ICP results. The weight of the obtained powder was 1.56 g. The weight percent of the surface modifying agents in the powder was 6.0 wt%, determined by TGA. Therefore, the yield of Ni 50 Co 50 -the amounts of Ni and Co atoms-was 99.5

We successfully prepared face-centered cubic (fcc) Cu-Ni (core-shell) nanoparticles by intramolecular reduction of formate complexes of Cu(2+) and Ni(2+) with long-chain amine ligands in a one-pot reaction within an extremely short time realized only under microwave irradiation. Observation by an HAADF-STEM technique showed that the nanostructure in one particle consisted of a Ni-rich shell and a Cu-rich core. Cu(4)Ni(6) nanoparticles with an average size of 11.7 nm were comprised of a Cu core with a diameter of ca. 6.0 nm, a Ni shell ca. 1.6 nm thick and a 0.9 nm thick interlayer of mixed Cu-Ni alloy between the Cu core and the Ni shell. Both the oxidation characteristics and the magnetic properties were dramatically affected by the molar ratios of Cu : Ni in the Cu-Ni nanoparticles. The magnetization of Cu(3)Ni(7) and Cu(4)Ni(6) comprised of a diamagnetic Cu-rich core, ferromagnetic Ni-rich shell and antiferromagnetic NiO-rich layer on the particle surface showed an exchange bias (209 and 143 Oe, respectively).

We have succeeded in rapidly preparing Ag core-Cu shell nanoparticles (denoted as Cu/Ag nanoparticles) having 10-40 nm in size by a microwave (MW)-assisted alcohol reduction process. The core-shell nanoparticles were prepared by step-bystep successive reduction of a silver precursor and then of a copper precursor added after the formation of silver nanoparticles in 1-heptanol.