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金属串配合物[CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt)结构和自旋过滤性质研究

吴子文 周沃华 丁丹丹 陈蓉 许旋 罗一帆 徐志广

吴子文, 周沃华, 丁丹丹, 陈蓉, 许旋, 罗一帆, 徐志广. 金属串配合物[CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt)结构和自旋过滤性质研究[J]. 华南师范大学学报(自然科学版), 2016, 48(1): 58-66.
引用本文: 吴子文, 周沃华, 丁丹丹, 陈蓉, 许旋, 罗一帆, 徐志广. 金属串配合物[CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt)结构和自旋过滤性质研究[J]. 华南师范大学学报(自然科学版), 2016, 48(1): 58-66.
Theoretical studies on the structures and spin filtering property of Metal String Complexes [CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt; dpa=dipyridylamide)[J]. Journal of South China normal University (Natural Science Edition), 2016, 48(1): 58-66.
Citation: Theoretical studies on the structures and spin filtering property of Metal String Complexes [CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt; dpa=dipyridylamide)[J]. Journal of South China normal University (Natural Science Edition), 2016, 48(1): 58-66.

金属串配合物[CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt)结构和自旋过滤性质研究

基金项目: 

广东省自然科学资金项目;广东省教育部产学研项目;广州市科技攻关项目

详细信息
    通讯作者:

    许旋

Theoretical studies on the structures and spin filtering property of Metal String Complexes [CoMCo(dpa)4(NCS)2](M=Co,Ni,Pd,Pt; dpa=dipyridylamide)

  • 摘要: 应用密度泛函理论B3LYP方法对金属串配合物[CoMCo(dpa)4(NCS)2](1:M=Co, 2:M=Ni, 3:M=Pd, 4:M=Pt; dpa=dipyridylamide)的成键性质和自旋过滤效应进行了研究,结果表明:配合物1的基态为二重态,Co36+金属链形成三中心三电子键(2nb1*0);而配合物2~4的基态均为反铁磁耦合单重态(AF态),对应的最低能量高自旋态(HS态)分别为三重态、七重态和七重态,单电子分布在两端Co原子上,[CoMCo]6+链具有三中心四电子键(2nb1*1)。由分子轨道能级图和PDOS图分析得到配合物1~4均具有自旋过滤效应,电子传输通道主要为-自旋nb轨道,与费米能级的距离大小为1234。电场作用下,1~4的高电势端Co2―N4键增长而低电势端Co3―N7键缩短,Co―M平均键长略为缩短,Co―M键增强;电场作用下金属原子的自旋密度和电荷密度变化很小,电磁性质稳定;电场作用下nb轨道分布仍保持沿金属轴方向离域,LUMO-HOMO能隙减小,有利于电子输运。
  • [1] Wu L P, Field P, Morrissey T, et al. Crystal Structure and Electronic Properties of Dibromo- and Dichloro- tetrakis [μ3-bis(2-pyridyl)amido] tricopper (II) Hydrate[J]. J. Chem. Soc., Dalton Trans., 1990, 12:3835-3840
    [2] Yang E C, Cheng M C, Tsai M S, et al. Structure of a linear unsymmetrical trinuclear cobalt(II) complex with a localized CoII-CoII bond: dichlorotetrakis[μ3-bis(2-pyridyl)amido] tricobalt(II)[J].J. Chem. Soc., Chem. Commun., 1994, 20:2377-2378
    [3] Clérac R, Cotton F A, Daniels L M, et al. Tuning the Metal-Metal Bonds in the Linear Tricobalt Compound Co3(dpa)4Cl2: Bond-Stretch and Spin-State Isomers[J]. Inorg. Chem., 2001, 40(6):1256-1264
    [4] Berry J F, Cotton F A, Murillo C A, et al. An Efficient Synthesis of Acetylide/Trimetal/Acetylide Molecular Wires[J]. Inorg. Chem., 2004, 43(7):2277-2283
    [5] Hsu L Y, Huang Q R, Jin B Y. Charge Transport Through a Single Molecular Wire Based on Linear Multimetal Complexes: A Non-Equilibrium Green's Function Approach[J].J. Phys. Chem. C., 2008, 112(28):10538-10541
    [6] Aduldecha S, Hathaway B. Crystal Structure and Electronic Properties of Tetrakis [μ3-bis (2-pyridyl)amido] dichlorotrinickel(II)-Water-Acetone (I /0.23/0.5)[J]. J. Chem. Soc., Dalton Trans., 1991, 4:993-998
    [7] Cotton F A, Daniels L M, Jordan G T I V. Efficient preparation of a linear, symmetrical, metal-metal bonded tricobalt compound; should we believe there is a bond stretch isomer?[J]. Chem. Commun., 1997, 5:421-422
    [8] Clérac R, Cotton F A, Jeffery S P, et al. Compounds with Symmetrical Tricobalt Chains Wrapped by Dipyridylamide Ligands and Cyanide or Isothiocyanate Ions as Terminal Ligands[J]. Inorg. Chem., 2001, 40(6):1265-1270
    [9] Berry J F, Cotton F A, Fewox C S, et al. Extended metal atom chains (EMACs) of five chromium or cobalt atoms: Symmetrical or unsymmetrical?[J]. Dalton Trans., 2004, 15:2297-2302
    [10]Rohmer M M, Liu I P C, Lin J C, et al. Structural, magnetic, and theoretical characterization of a heterometallic polypyridylamide complex[J]. Angew. Chem., Int. Ed., 2007, 46(19):3533-3536
    [11]Liu I P C, Lee G H, Peng S M, et al. Cu-Pd-Cu and Cu-Pt-Cu Linear Frameworks: Synthesis, Magnetic Properties, and Theoretical Analysis of Two Mixed-Metal Complexes of Dipyridylamide(dpa), Isostructural, and Isoelectronic with [Cu3 (dpa)4Cl2]+[J]. Inorg. Chem., 2007, 46(23):9602-9608.
    [12]Kuo J H, Tsao T B, Lee G H, et al. An Extended Metal Chain with the 2,7-Bis(dipyridyldiamino)-1,8-naphthyridine (H4bdpdany) Ligand - The Longest Even-Numbered Metal Chain Complex[J]. Eur. J. Inorg. Chem., 2011, 13:2025-2028
    [13]Lin S Y, Chen I W P, Chen C H, et al. Effect of Metal-Metal Interactions on Electron Transfer: an STM Study of One-Dimensional Metal String Complexes[J]. J. Phys. Chem. B., 2004, 108(3):959-964
    [14]Chen I W P, Fu M D, Tseng W H, et al. Conductance and Stochastic Switching of Ligand-Supported Linear Chains of Metal Atoms[J]. Angew. Chem. Ger Ed., 2006, 118(35):5946-5949
    [15]Georgiev V P, McGrady J E. Efficient Spin Filtering through Cobalt-Based Extended Metal Atom Chains[J]. Inorg. Chem., 2010, 49(12):5591-5597
    [16]Georgiev V P, Sameera W M C, McGrady J E. Attenuation of Conductance in Cobalt Extended Metal Atom Chains[J]. J. Phys. Chem. C., 2012, 116(38):20163-20172
    [17]Tabookht Z, de G C, López X. Towards a low-spin configuration in extended metal atom chains. Theoretical study of trimetallic systems with 22 metal electrons[J]. Dalton Trans., 2012, 41:498-504.
    [18]Luo K G, Tan Y, Xu X, et al. Theoretical studies on the structures of one-dimensional Nin (n=3, 5, 7) metal string complexes under the effect of electric field[J]. Inorg. Chim. Acta., 2014, 421(2):310-317.
    [19]黄晓, 谭莹, 许旋, 等. 电场对杂金属串配合物[CuCuM(npa)4Cl]+ (M=Pt, Pd, Ni)结构影响的理论研究[J].化学学报 2012, 70:1979-1986
    HUANG X, TAN Y, XU X, et a l. Theoretical Studies on Structures of Heterometal String Complexes[CuCuM(npa)4Cl]+ (M=Pt, Pd, Ni) under the Electric Field[J]. ActaChim. Sin. 2012, 70:1979-1986
    [20]黄燕, 黄晓, 许旋, 等. 电场对M3(dpa)4Cl2(M=Co, Rh, Ir)金属串配合物结构影响的理论研究[J].物理化学学报 2013, 29(6):1225-1232
    HUANG Y, HUANG X, XU X, et al. Effects of Electric Field on the Structures of Metal String ComplexesM3(dpa)4Cl2 (M=Co, Rh, Ir; dpa=dipyridylamide)[J].Acta Phys. Chim. Sin. 2013, 29(6):1225-1232
    [21]Ginsberg A P. Magnetic exchange in transition metal complexes. 12. Calculation of cluster exchange coupling constants with the Xα-scattered wave method[J]. J. Am. Chem. Soc., 1980, 102(1):111-117
    [22]Noodleman L. Valence bond description of antiferromagnetic coupling in transition metal dimers[J].J. Chem. Phys., 1981, 74(10):5737-5743
    [23]Glendening E D. Reed A E. Carpenter, J. E. NBO Version 3.1[CP].
    [24]Lu T, Chen F. Multiwfn: A multifunctional wavefunction analyzer[J]. J. Comput. Chem., 2012, 33(5):580-592
    [25]Frisch M, Trucks G, Schlegel H B, et al. Gaussian 09, Revision B.01; Gaussian Inc.: Pittsburgh, PA, 2009[CP].
    [26]Kitagawa Y, Matsui T, Nakanishi Y, et al. Theoretical studies of electronic structures, magnetic properties and electron conductivities of one-dimensional Nin (n=3, 5, 7) complexes[J]. Dalton Trans., 2013, 42(45):16200-16208.
    [27] Moodera J S, Hao X, Gibson G A, et al. Electron-Spin Polarization in Tunnel Junctions in Zero Applied Field with Ferromagnetic EuS Barriers[J]. Phys. Rev. Lett., 1988, 61(5):637-640
    [28]Tsai T W, Huang Q R, Peng S M, et al. Smallest electrical wire based on extended metal-atom chains[J]. J. Phys. Chem. C., 2010, 114(8):3641-3644

    [1] Wu L P, Field P, Morrissey T, et al. Crystal Structure and Electronic Properties of Dibromo- and Dichloro- tetrakis [μ3-bis(2-pyridyl)amido] tricopper (II) Hydrate[J]. J. Chem. Soc., Dalton Trans., 1990, 12:3835-3840
    [2] Yang E C, Cheng M C, Tsai M S, et al. Structure of a linear unsymmetrical trinuclear cobalt(II) complex with a localized CoII-CoII bond: dichlorotetrakis[μ3-bis(2-pyridyl)amido] tricobalt(II)[J].J. Chem. Soc., Chem. Commun., 1994, 20:2377-2378
    [3] Clérac R, Cotton F A, Daniels L M, et al. Tuning the Metal-Metal Bonds in the Linear Tricobalt Compound Co3(dpa)4Cl2: Bond-Stretch and Spin-State Isomers[J]. Inorg. Chem., 2001, 40(6):1256-1264
    [4] Berry J F, Cotton F A, Murillo C A, et al. An Efficient Synthesis of Acetylide/Trimetal/Acetylide Molecular Wires[J]. Inorg. Chem., 2004, 43(7):2277-2283
    [5] Hsu L Y, Huang Q R, Jin B Y. Charge Transport Through a Single Molecular Wire Based on Linear Multimetal Complexes: A Non-Equilibrium Green's Function Approach[J].J. Phys. Chem. C., 2008, 112(28):10538-10541
    [6] Aduldecha S, Hathaway B. Crystal Structure and Electronic Properties of Tetrakis [μ3-bis (2-pyridyl)amido] dichlorotrinickel(II)-Water-Acetone (I /0.23/0.5)[J]. J. Chem. Soc., Dalton Trans., 1991, 4:993-998
    [7] Cotton F A, Daniels L M, Jordan G T I V. Efficient preparation of a linear, symmetrical, metal-metal bonded tricobalt compound; should we believe there is a bond stretch isomer?[J]. Chem. Commun., 1997, 5:421-422
    [8] Clérac R, Cotton F A, Jeffery S P, et al. Compounds with Symmetrical Tricobalt Chains Wrapped by Dipyridylamide Ligands and Cyanide or Isothiocyanate Ions as Terminal Ligands[J]. Inorg. Chem., 2001, 40(6):1265-1270
    [9] Berry J F, Cotton F A, Fewox C S, et al. Extended metal atom chains (EMACs) of five chromium or cobalt atoms: Symmetrical or unsymmetrical?[J]. Dalton Trans., 2004, 15:2297-2302
    [10]Rohmer M M, Liu I P C, Lin J C, et al. Structural, magnetic, and theoretical characterization of a heterometallic polypyridylamide complex[J]. Angew. Chem., Int. Ed., 2007, 46(19):3533-3536
    [11]Liu I P C, Lee G H, Peng S M, et al. Cu-Pd-Cu and Cu-Pt-Cu Linear Frameworks: Synthesis, Magnetic Properties, and Theoretical Analysis of Two Mixed-Metal Complexes of Dipyridylamide(dpa), Isostructural, and Isoelectronic with [Cu3 (dpa)4Cl2]+[J]. Inorg. Chem., 2007, 46(23):9602-9608.
    [12]Kuo J H, Tsao T B, Lee G H, et al. An Extended Metal Chain with the 2,7-Bis(dipyridyldiamino)-1,8-naphthyridine (H4bdpdany) Ligand - The Longest Even-Numbered Metal Chain Complex[J]. Eur. J. Inorg. Chem., 2011, 13:2025-2028
    [13]Lin S Y, Chen I W P, Chen C H, et al. Effect of Metal-Metal Interactions on Electron Transfer: an STM Study of One-Dimensional Metal String Complexes[J]. J. Phys. Chem. B., 2004, 108(3):959-964
    [14]Chen I W P, Fu M D, Tseng W H, et al. Conductance and Stochastic Switching of Ligand-Supported Linear Chains of Metal Atoms[J]. Angew. Chem. Ger Ed., 2006, 118(35):5946-5949
    [15]Georgiev V P, McGrady J E. Efficient Spin Filtering through Cobalt-Based Extended Metal Atom Chains[J]. Inorg. Chem., 2010, 49(12):5591-5597
    [16]Georgiev V P, Sameera W M C, McGrady J E. Attenuation of Conductance in Cobalt Extended Metal Atom Chains[J]. J. Phys. Chem. C., 2012, 116(38):20163-20172
    [17]Tabookht Z, de G C, López X. Towards a low-spin configuration in extended metal atom chains. Theoretical study of trimetallic systems with 22 metal electrons[J]. Dalton Trans., 2012, 41:498-504.
    [18]Luo K G, Tan Y, Xu X, et al. Theoretical studies on the structures of one-dimensional Nin (n=3, 5, 7) metal string complexes under the effect of electric field[J]. Inorg. Chim. Acta., 2014, 421(2):310-317.
    [19]黄晓, 谭莹, 许旋, 等. 电场对杂金属串配合物[CuCuM(npa)4Cl]+ (M=Pt, Pd, Ni)结构影响的理论研究[J].化学学报 2012, 70:1979-1986
    HUANG X, TAN Y, XU X, et a l. Theoretical Studies on Structures of Heterometal String Complexes[CuCuM(npa)4Cl]+ (M=Pt, Pd, Ni) under the Electric Field[J]. ActaChim. Sin. 2012, 70:1979-1986
    [20]黄燕, 黄晓, 许旋, 等. 电场对M3(dpa)4Cl2(M=Co, Rh, Ir)金属串配合物结构影响的理论研究[J].物理化学学报 2013, 29(6):1225-1232
    HUANG Y, HUANG X, XU X, et al. Effects of Electric Field on the Structures of Metal String ComplexesM3(dpa)4Cl2 (M=Co, Rh, Ir; dpa=dipyridylamide)[J].Acta Phys. Chim. Sin. 2013, 29(6):1225-1232
    [21]Ginsberg A P. Magnetic exchange in transition metal complexes. 12. Calculation of cluster exchange coupling constants with the Xα-scattered wave method[J]. J. Am. Chem. Soc., 1980, 102(1):111-117
    [22]Noodleman L. Valence bond description of antiferromagnetic coupling in transition metal dimers[J].J. Chem. Phys., 1981, 74(10):5737-5743
    [23]Glendening E D. Reed A E. Carpenter, J. E. NBO Version 3.1[CP].
    [24]Lu T, Chen F. Multiwfn: A multifunctional wavefunction analyzer[J]. J. Comput. Chem., 2012, 33(5):580-592
    [25]Frisch M, Trucks G, Schlegel H B, et al. Gaussian 09, Revision B.01; Gaussian Inc.: Pittsburgh, PA, 2009[CP].
    [26]Kitagawa Y, Matsui T, Nakanishi Y, et al. Theoretical studies of electronic structures, magnetic properties and electron conductivities of one-dimensional Nin (n=3, 5, 7) complexes[J]. Dalton Trans., 2013, 42(45):16200-16208.
    [27] Moodera J S, Hao X, Gibson G A, et al. Electron-Spin Polarization in Tunnel Junctions in Zero Applied Field with Ferromagnetic EuS Barriers[J]. Phys. Rev. Lett., 1988, 61(5):637-640
    [28]Tsai T W, Huang Q R, Peng S M, et al. Smallest electrical wire based on extended metal-atom chains[J]. J. Phys. Chem. C., 2010, 114(8):3641-3644

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  • 收稿日期:  2015-05-13
  • 修回日期:  2015-05-26
  • 刊出日期:  2016-01-25

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