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)
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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。
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Abstract: The bonding and spin filtering properties of metal string complexes [CoMCo(dpa)4(NCS)2](M=Co, Ni, Pd, Pt; dpa=dipyridylamide) have been investigated with density functional theory B3LYP method. The results show that: the ground state of complex 1 is doublet, there is a 3-center-3-electron bond delocalized over the Co36+ chain. However, the ground states of complexes 2~4 are antiferromagnetic(AF) singlet, corresponded to the high spin configurations with two unpaired, six unpaired and six unpaired electrons, respectively. The unpaired electrons of complexes 2~4 largely localize on the termimal CoII ions and there is a 3-center-4-electron bond delocalized over the [CoMCo]6+ chain. The molecular orbital energy level diagrams and PDOS diagrams show that the spin- components of singly nb orbital are the dominant transport channel. Complexes 1~4 all possess spin filtering effect. The distance between spin- components of nb orbital and Fermi levels is 1234. Under the electric field, the Co2―N4 bond lengths at the high potential side increase, while the Co3―N7 distances at the low potential side tend to be shortened. The average Co―M distances, the spin densities and NPA charge of metal atoms are less affected by electric field, indicating the electromagnetic properties are stable. Under the electric field, the nb orbital still keeps delocalized along the metal chain and the LUMO-HOMO gaps decrease. This is beneficial for electron transfer.-
Keywords:
- Broken symmetry
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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
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[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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