本論文研究Ru2(OAc)4Cl雙核金屬錯合物與Ru2Ni(dpa)4Cl2、[Ru2Ni(dpa)4Cl2]PF6與Ru2Ni(dpa)4(NCS)2 (dpa=di-pyridyl-amine)直線型三核混金屬串錯合物與Ru2M3(tpda)4(NCS)2 (M = Ni、Co) (tpda=tri-pyridyl-diamine)直線型五核混金屬串錯合物分子的振動模式，以了解其中過渡金屬(Ru、Ni、Co)中所帶價數。我們利用He-Ne雷射(632.8 nm)以及Nd-YAG(532 nm)為激發光源及高解析拉曼光譜系統，測量了雙核金屬錯合物、直線型三核混金屬串錯合物和直線型五核混金屬串錯合物的拉曼與表面增強拉曼光譜(SERS)，配合紅外光吸收光譜與理論計算結果，對直線型三核與五核異核混金屬串錯合物中[Ru2]之價數進行指認。在異核混金屬串分子的表面增強拉曼光譜(SERS)中，我們發現其與固態拉曼光譜比較的結果，發現其光譜位置會受到金屬奈米粒子表面熱電子的影響，造成異核金屬串會氧化還原。我們以Ru2(OAc)4Cl 中[Ru2]5+之電子組態為(σ)2(π)4(δ)2(δ*)1(π*)2 Ru-Ru間振動頻率為327 cm-1，在金奈米粒子中還原成[Ru2]4+ Ru-Ru間振動頻率為321 cm-1，在銀奈米粒子中氧化成[Ru2]6+Ru-Ru間振動頻率為337 cm-1。由上述所指認之[Ru2]價數及其 Ru-Ru間振動頻率，[Ru2Ni(dpa)4Cl2]0,1+和Ru2Ni(dpa)4(NCS)2中固態拉曼光譜Ru-Ru間振動頻率為327cm-1 、333 cm-1及325 cm-1 [Ru2]價數被指認為+5、+5.5、+5，而[NiRu2Ni2(tpda)4(NCS)2]0，1+ 中固態拉曼光譜Ru-Ru間振動頻率為337cm-1 及335 cm-1 [Ru2]價數被指認為+6和+6，[Ru2Co3(tpda)4(NCS)2]0，1+中固態拉曼光譜Ru-Ru間振動頻率為320 cm-1及319 cm-1[Ru2]價數被指認為+4和+4 。

Surface enhanced Raman scattering (SERS) spectra of heterometal extended metal atom chain (EMAC) complexes diruthenium nickel dipyridylamide [Ru2Ni(dpa)4Cl2]0,1+ display Ru-Ru stretching band at 312 cm-1. However, these bands obtained in solid form are at 327 and 333 cm-1 for the neutral and oxidized complexes, respectively. In these EMACs, moiety ruthenium dimer has charge [Ru2]+5 and nickel has charge Ni+1 and Ni+2, respectively. Hence, their Ru-Ru stretching wavenumbers are similar. When the thiol molecule 3-mercaptopropionic acid was used to cover the surface of nanoparticle the band positions are blue shifted to those in solid form. The hot electron was proposed to be produced when the surface plasmon band of nanoparticle is excited. The electron configuration of moiety [Ru2]+5 is (σ)2(π)4(δ)2(δ*)1(π*)2 thus the bond order is 2.5. When reduction occurs, one extra electron fills in the antibonding orbital weakening the Ru-Ru bonding. For both EMAC complexes ruthenium is reduced to [Ru2]+4 and the Ru-Ru stretching is about 321 cm-1. When oxidation occurs, one electron removed from antibonding orbital strengthen the Ru-Ru bonding. For both EMAC complexes ruthenium is oxidation to [Ru2]+6 and the Ru-Ru stretching is about 337 cm-1. So we can identified the valence of transition metal in the heterometal extended metal atom chain (EMAC) complexes diruthenium nickel dipyridylamide.

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