Electron Transport of Metal String Complexes of [MM'M″(dpa)4(Cl)2](M=Co, Ni; M',M″=Co, Rh)†

doi:10.7503/cjcu20180804

Abstract

Abstract:

The electronic structures and transmission properties of metal string complexes [MM'M″(dpa)₄·(Cl)₂][MM'M″=CoCoCo(1); CoCoRh(2); CoRhRh(3); NiCoRh(4)] were investigated by density functional theory BP86 method. The results show that there is a delocalized 3-center-3-lectron σ bond of (MM'M″)⁶⁺ among complexes 1, 2 and 4, while there are one delocalized 3-center-4-electron σ bond of (MM'M″)⁶⁺ and two 3-center-5-electron π bonds in complex 3. The Rh—Rh bond of complex 3 is the strongest among complexes 1—4 and the Co—Rh bond is second on account of above-mentioned information. The substitution of Rh enhanced the M—M bond, and the replace of Ni weakened the M—M bond. In conclusion, the order of bond is Rh—Rh>Co—Rh>Co—Co>Ni—Co. The transport channels of complexes 1—4 contain π-type and σ-type orbitals. Under positive bias, the currents in complexes 2 and 3 are greater than complexes 1 and 4. Under negative bias, there is a negative differential resistance effect in complex 4. The energy splitting of σ_nbα/β and π^*α/β orbit as transport channels in complex 3 are the most obvious among complexes 1—4. Moreover, the contribution of (MM'M″)⁶⁺ to the π^* orbit of β spin(up to 88%) is larger than that of α (up to 74%). Thus, the electronic transmission of β spin channel is stronger than α spin. To sum up, the complex 3 has significant spin filter effect (up to 70%—80%).

Key words: Metal string complex, Density functional theory(DFT), Electronic transport, Spin filter effect

CLC Number:

O641

TrendMD:

ZHI Shasha,BAN Ying,XU Zhiguang,XU Xuan. Electron Transport of Metal String Complexes of [MM'M″(dpa)₄(Cl)₂](M=Co, Ni; M',M″=Co, Rh)^†[J]. Chem. J. Chinese Universities, 2019, 40(5): 980.

Figures/Tables 9

Fig.1 Sketch structure for complexes 1—4(A) and the device of external bias(B)

Fig.2 Structural diagrams of complexes 1(A), 2(B), 3(C) and 4(D) with bond lengths(nm) and wiberg bond order in parentheses calculated by BP86 method

Fig.3 Diagram of molecular orbital energy levels for complexes 2(A), 3(B) and 4(C) The dotted line indicates the fermi energy of the gold electrode.

Fig.4 Transmission spectra of complex 1 under the potential of 0 V(A), 0.1 V(B), 0.2 V(C), 0.3 V(D) and 0.5 V(E) Fermi energy is set to be 0. Black and red line denote the spin-α and spin-β manifolds, respectively.

Fig.5 Transmission spectra of complex 2 under the potential of -0.5 V(A), -0.3 V(B), -0.2 V(C), 0 V(D), 0.2 V(E), 0.3 V(F) and 0.5 V(G) Fermi energy is set to be 0. Black and red line denote the spin-α and spin-β manifolds, respectively.

Fig.6 Transmission spectra of complex 3 under the potential of -0.5 V(A), -0.3 V(B), -0.2 V(C), 0 V(D), 0.2 V(E), 0.3 V(F) and 0.5 V(G) Fermi energy is set to be 0. Black and red line denote the spin-α and spin-β manifolds, respectively.

Fig.7 Transmission spectra of complex 4 under the potential of -0.5 V(A), -0.3 V(B), -0.2 V(C), 0 V(D), 0.2 V(E), 0.3 V(F) and 0.5 V(G) Fermi energy is set to be 0. Black and red line denote the spin-α and spin-β manifolds, respectively.

Fig.8 Spatial distribution of π MOs under electric field of complex 3

Fig.9 Computed current-voltage charateristics of complexes 1(A), 2(B), 3(C) and 4(D)

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Electron Transport of Metal String Complexes of [MM'M″(dpa)₄(Cl)₂](M=Co, Ni; M',M″=Co, Rh)^†

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