金属串配合物[Cr3(dpa)4LL'](dpa=dipyridylamide; L, L'=Cl, BF4, CCPh)的Cr

引用本文: 马华璇, 郑燕玲, 詹益仕, 谭莹, 黄晓, 彭琦, 许旋. 金属串配合物[Cr₃(dpa)₄LL'](dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)的Cr—Cr成键特性[J]. 物理化学学报, 2012, 28(07): 1637-1644. doi: 10.3866/PKU.WHXB201204111 shu

Citation: MA Hua-Xuan, ZHENG Yan-Ling, ZHAN Yi-Shi, TAN Ying, HUANG Xiao, PENG Qi, XU Xuan. The Cr—Cr Bonding Character in Metal String Complexes [Cr₃(dpa)₄LL'] (dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)[J]. Acta Physico-Chimica Sinica, 2012, 28(07): 1637-1644. doi: 10.3866/PKU.WHXB201204111 shu

金属串配合物[Cr₃(dpa)₄LL'](dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)的Cr—Cr成键特性

马华璇 ^1, ,
郑燕玲 ^1, ,
詹益仕 ^1, ,
谭莹 ^1, ,
黄晓 ^1, ,
彭琦 ^1, ,
许旋 ^1,2,3,4,

基金项目:
广东省自然科学资金项目(9151063101000037) (9151063101000037)

广东省教育部产学研项目(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)

摘要:

采用密度泛函理论UBP86方法计算了Cr₃(dpa)₄Cl₂ (1)、Cr₃(dpa)₄(BF₄)₂ (2)、Cr₃(dpa)₄Cl(BF₄) (3)、Cr₃(dpa)₄(CCPh)₂ (4)和Cr₃(dpa)₄Cl(CCPh) (5)金属串配合物的结构, 并对配合物的构型、Cr—Cr键的本质以及轴向配体对Cr—Cr键的影响进行了研究. 结果表明: (1) Cr—Cr平均键长较长的配合物趋于形成对称构型, 较短时趋于形成非对称构型. 最稳定的五重态的Cr—Cr平均键长最长, 故优化时趋于形成对称构型; 七重态的Cr—Cr平均键长最短, 趋于形成非对称构型; (2) 五重态的Cr₃⁶⁺金属链均存在三中心三电子σ键, 含弱σ给电子轴向配体BF₄^-的2和3的Cr—Cr短键还具有弱的π相互作用. 七重态下, 对称构型的4中仅有三中心三电子σ键, 而非对称构型的1-3、5的Cr—Cr短键为三重键, 非对称构型仍具有Cr₃⁶⁺链的σ离域作用, 仍具有分子导线的潜在应用; (3) 轴向配体L与Cr的作用主要表现为n_L→4_{s_Cr}或n_L→3_dz²Cr离域, 较强的σ给电子配体CCPh^-还存在σ_C—C→4_{s_Cr}离域. Cr与L的结合强度为2＜3＜1＜5＜4, CCPh^-与Cr的结合最强, 使Cr—Cr键减弱、Cr—Cr距离增长, 故4的各自旋重态均为对称构型.

关键词:

English

The Cr—Cr Bonding Character in Metal String Complexes [Cr₃(dpa)₄LL'] (dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)

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: 23 February 2012
Available Online: 07 June 2012
Fund Project:
广东省自然科学资金项目(9151063101000037)

广东省教育部产学研项目(2010B090400184)

广东省人才引进专项资金(C10133)

广州市科技攻关项目(2011J4300063)资助

Abstract:

To study the configuration, the metal-metal interactions and the influences of axial ligands L and L' on the Cr—Cr bond in metal string complexes Cr₃(dpa)₄LL' (L, L'=Cl, BF₄, CCPh), the structures of complexes Cr₃(dpa)₄Cl₂ (1), Cr₃(dpa)₄(BF₄)2 (2), Cr₃(dpa)₄Cl(BF₄) (3), Cr₃(dpa)₄(CCPh)2 (4) and Cr₃(dpa)₄Cl(CCPh) (5) were investigated by density functional theory UBP86 method. The conclusions can be drawn as follows: (1) The complex with longer average Cr—Cr distance tends to form a symmetrical configuration, while it tends to form a asymmetric configuration with shorter average Cr—Cr distance. The most stable spin states, quintet states, with the longest average Cr—Cr distance tend to form a symmetrical configuration, while septuplet states with shortest Cr—Cr distance tend to form asymmetrical one; (2) For quintet states of all complexes, there is only a 3-center-3-electron σ bond in Cr₃⁶⁺ chain. Furthermore, except the σ bond, there are weak π Cr—Cr interactions in complex 2 and 3. For septuplet states, there is a triple bond in the short Cr—Cr bond of complexes 1-3 and 5, while there is only a 3-center-3-electron σ bond in complex 4. Not only in symmetrical configuration but also in asymmetric configuration, there are σ delocalizations in Cr₃⁶⁺ chain, suggesting the asymmetrical metal string complexes are still the potential molecular wire species; (3) The interactions between axial ligand L and Cr atom mainly correspond to the n_L→4_{s_Cr} and n_L→3_dz²Cr delocalizations. In addition, for stronger σ donor CCPh^- ligand, there are σ_C—C→4_{s_Cr} delocalizations as well. The order of the bond strength of axial ligand L and Cr atom is 2＜3＜1＜5＜4. The strongest bonding between CCPh^- ligand and Cr atom weakens the Cr—Cr bond and lengthens the Cr—Cr distance. Therefore, every spin state of 4 tends to form a symmetrical configuration.

Key words:

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金属串配合物[Cr₃(dpa)₄LL'](dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)的Cr—Cr成键特性

English

The Cr—Cr Bonding Character in Metal String Complexes [Cr₃(dpa)₄LL'] (dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)

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