Citation: HUANG Yan, HUANG Xiao, XU Xuan. Effects of Electric Field on the Structures of Metal String Complexes M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201303181 shu

Effects of Electric Field on the Structures of Metal String Complexes M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)

HUANG Yan ¹ ,
HUANG Xiao ¹ ,
XU Xuan ^1,2,3,4,

1.
1 School of Chemistry & Environment, South China Normal University, Guangzhou 510006, P. R. China;
2 Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006, P. R. China;
3 Key Laboratory of Electrochemical Technology on Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006, P. R. China;
4 Engineering Research Center of Materials and Technology for Electrochemical Energy Storage, Ministry of Education, South China Normal University, Guangzhou 510006, P. R. China

Received Date: 16 November 2012
Available Online: 18 March 2013
Fund Project: 广东省自然科学基金项目(S2012010008763) (S2012010008763)广东省教育部产学研结合项目(2010B090400184) (2010B090400184)广东省人才引进专项资金(C10133) (C10133)广州市科技攻关项目(2011J4300063)资助 (2011J4300063)

As potential molecular wire species, the geometrical and electronic structures of metal string complexes M₃(dpa)₄Cl₂ (1: M=Co, 2: M=Rh, 3: M=Ir; dpa=dipyridylamide) were investigated theoretically using density functional theory with the PBE0 functional by considering the interaction of an external electric field along the M₃⁶⁺ linear metal chain. The results show that the ground states of the complexes are all doublets. There is a 3-center-3-electron σ bond delocalized over the M₃⁶⁺ chain for 1 and 2, while there is a 3-center-4-electron σ bond and a weak δ bond among the Ir₃⁶⁺ chain in 3. Moving down the column of Co, Rh, and Ir elements in the periodic table, the complexes with the corresponding metals showed some regular trends, such as stronger M－M bonds, smaller LUMO-HOMO gaps, weaker anti-ferromagnetic spin coupling among the M₃⁶⁺ chains, and stronger spin delocalization from M₃⁶⁺ to ligands. In the external electric field along the Cl4→Cl5 direction, the M3 ― Cl5 bonds at the low potential side tend to be shortened, while the M2―Cl4 distances at the high potential side increase. With the increase of electric field, the average M―M distances slightly decrease, which is beneficial for electron transport. When the electric field increases, the molecular energy decreases and the dipole moment linearly increases. Moreover, the negative charge moves from Cl5 at the low potential end towards Cl4 at the high potential end, and the spin electron moves from M3 at the low potential end to M1 and M2 at the high potential end, while the positive charges transfer in the opposite direction along the M₃⁶⁺ chain of 3. However, there is no charge transfer between dpa^- ligands and M₃⁶⁺ chain or Cl^- ligands. The LUMO-HOMO gaps decrease with increasing electric field, which is beneficial for electron transfer. The sensitivity of the frontier orbitals to the electric field is different, which leads to the orbital level crossing for LUMO or HOMO. Moving down the column of metal elements in the periodic table, the complexes with the corresponding metals showed weaker orbital level crossing for LUMO or HOMO and smaller deviation of average M―M distances due to the effect of the electric field.
- Metal string complex,
- Density functional theory,
- Electric field effect,
- Molecular wire,
- Metal-metal interaction
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Effects of Electric Field on the Structures of Metal String Complexes M3(dpa)4Cl2 (M=Co, Rh, Ir; dpa=dipyridylamide)

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Effects of Electric Field on the Structures of Metal String Complexes M₃(dpa)₄Cl₂ (M=Co, Rh, Ir; dpa=dipyridylamide)