Recent Progresses in ESR Studies on Ferrocenyl Compounds

  • YANG Xian-peng ,
  • YU Hao-jie ,
  • WANG Li
Expand
  • State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

Received date: 2015-08-20

  Revised date: 2016-07-08

  Online published: 2016-09-05

Abstract

Ferrocenyl compounds were widely used and extensively studied due to their excellent thermal, redox, electronic, optic, magnetic and catalytic properties. Electron spin resonance (ESR) is a method that can be used to study paramagnetic behaviors, electronic structure, electron transfer and molecular interactions of ferrocenyl compounds. In addition, ESR possesses advantages such as high sensitivity, easy sample treatment and nondestructive testing. This article reviewed recent progresses in ESR studies on ferrocenyl compounds.

Cite this article

YANG Xian-peng , YU Hao-jie , WANG Li . Recent Progresses in ESR Studies on Ferrocenyl Compounds[J]. Chinese Journal of Magnetic Resonance, 2016 , 33(3) : 491 -501 . DOI: 10.11938/cjmr20160314

References

[1] Yang Yin(杨茵), Chen Jia-liang(陈家良), Su Xun-cheng(苏循成), et al. Paramagnetic labeling of proteins and pseudocontact shift in structural biology(蛋白质顺磁标记技术与生物核磁共振中的赝接触位移)[J]. Chinese J Magn Reson(波谱学杂志), 2014, 31(2): 155-171.

[2] Zhao Bao-lu(赵保路). “Double edge” effects of nitric oxide free radical in cardio-brain-vascular diseases and health studied by ESR[利用电子自旋共振(ESR)技术研究一氧化氮自由基在心脑血管疾病和健康中的“双刃剑”作用][J]. Chinese J Magn Reson(波谱学杂志), 2015, 32(2): 195-207.

[3] Elschenbroich C, Bilger E, Ernst R D, et al. Closed, half open, and open ferrocenes redox behavior and electron spin resonance of the radical cations[J]. Organometallics, 1985, 4(11): 2 068-2 071.

[4] Jana R, Mobin S M, Schwederski B, et al. Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(I) complexes: Structures and spectroelectrochemical behaviour[J]. Dalton Trans, 2013, 42(45): 16 142-16 150.

[5] Dong T Y, Hendrickson D N, Pierpont C G, et al. Mixed-valence 1',6'-Dihalobiferrocenium salts - the effect of the solid-state environment on electron-transfer rates[J]. J Am Chem Soc, 1986, 108(5): 963-971.

[6] Prins R. Electronic structure of the ferricenium cation: Electron spin resonance measurements of the cations of ferrocene derivatives[J]. Mol Phys, 1970, 19(5): 603-620.

[7] Prins R, Reinders F J. Electron spin resonance of the cation of ferrocene[J]. J Am Chem Soc, 1969, 91(17): 4 929-4 931.

[8] Duggan D M, Hendrickson D N. Electronic structure of various ferricenium systems as inferred from raman, infrared, low-temperature electronic absorption, and electron paramagnetic resonance measurements[J]. Inorg Chem, 1975, 15(4): 955-970.

[9] Prins R, Korswagen A R. Substituent effects in the ESR spectra of ferricenium cations[J]. J Organomet Chem. 1970, 25(2): C74-C76.

[10] Siebler D, Gasi T, Heinze K. Biferrocene amino acid, a ferrocenylogoue of ferrocene amino acid: Synthesis, cross-linking, and redox chemistry[J]. Organometallics, 2011, 30(2): 313-327.

[11] Cowan D O, Candela G A, Kaufman F. Organic solid state. V. symmetry distortions in ferrocenium compounds[J]. J Am Chem Soc, 1971, 93(16): 3 889-3 893.

[12] Lohan M, Ecorchard P, Lapinte C, et al. 1',1'''-Bis(ethynyl) biferrocene as a linking group for gold, ruthenium, and osmium fragments: Synthesis, solid state structures, and electrochemical, UV-Vis, and EPR spectroscopical studies[J]. Organometallics, 2009, 28(6): 1 878-1 890.

[13] Dong T Y, Schei C C, Hwang M Y, et al. Pronounced effect of substituents on the intramolecular electron-transfer rates in mixed-valence biferrocenium triiodide complexes[J]. Organometallics, 1992, 11(2): 573-582.

[14] Dong T, Chang L, Lee G, et al. Pronounced effects of zero-point energy difference on intramolecular[J]. Organometallics, 2002, 21(20): 4 192-4 200.

[15] Rao Y, Kusamoto T, Sakamoto R, et al. Reactivity and electronic properties of a ferrocene molecule bearing an N,C-chelated BMes[J]. Organometallics, 2014, 33(7): 1 787-1 793.

[16] Kusamoto T, Takada K, Sakamoto R, et al. Ferrocene-dithiolene hybrids: Control of strong donor-acceptor electronic communication to reverse the charge transfer direction[J]. Inorg Chem, 2012, 51(22): 12 102-12 113.

[17] Sixt T, Sieger M, Krafft M J, et al. Ambi-valence taken literally: Ruthenium vs iron oxidation in (1,1'-diphosphinoferrocene) ruthenium(II) hydride and chloride complexes as deduced from spectroelectrochemistry of the heterodimetallic “mixed-valent” intermediates[J]. Organometallics, 2010, 29(21): 5 511-5 516.

[18] Toda Y, Ishimaru S I, Ikeda R, et al. Oxidation of ferrocene molecules adsorbed in MCM-41[J]. J Phys Chem Solids, 2004, 65(2, 3): 471-473.

[19] Ward H R, Lawler R G, Loken H Y, et al. Nuclear polarization in the products of chemical reactions occurring in the absence of a magnetic field[J]. J Am Chem Soc, 1969, 91(17): 4 928-4 929.

[20] Schnitzler M C, Mangrich A S, Macedo W A A, et al. Incorporation, oxidation and pyrolysis of ferrocene into porous silica glass: a route to different silica/carbon and silica/iron oxide nanocomposites[J]. Inorg Chem, 2006, 45(26): 10 642-10 650.

[21] Wang L, Wang X J, Pan J, et al. Study on ESR spectra of poly(ferrocenyldimethylsilane)/TCNE and spin-probed poly (ferrocenyldimethylsilane)[J]. J Appl Polym Sci, 2002, 86(14): 3 508-3 511.

[22] Tanaka H, Mizota K. Generation of a spin polymer through a charge-transfer complex of a ferrocenyl mesogen with tetracyanoethylene in the solid state[J]. Macromol Rapid Comm, 1995, 16(1): 1-7.

[23] Kuroda H. Polarized absorption spectra of single crystals of ferrocene and its molecular complexes[J]. J Mol Spectrosc, 1969, 30(1-3): 355-364.

[24] Adman E, Rosenblum M, Sullivan S, et al. Structure of the ferrocene-tetracyanoethylene complex[J]. J Am Chem Soc, 1967, 17(89): 4 540-4 542.

[25] Yan Y, Li B, He Q, et al. Synthesis and redox-responsive self-assembly of ferrocene grafted anderson-type polyoxometalate hybrid complexes[J]. Soft Matter, 2012, 8(5): 1 593-1 600.

[26] Fukuzumi S, Okamoto K, Imahori H. Thermal intramolecular electron transfer in a ferrocene-naphthoquinone linked dyad promoted by metal ions[J]. Angew Chem Int Ed, 2002, 41(4): 620-622.

[27] Song L X, Du F Y, Yang J, et al. Fc-content dependence of composition, structure and degradation degree in supramolecular aggregates of polypropylene glycol, ferrocene and β-cyclodextrin[J]. Soft Matter, 2011, 7(14): 6 671-6 677.

[28] Elschenbroich C, Plackmeyer J, Nowotny M, et al. Electro- and magnetocommunication in [5,5]ditrovacenyls, [(η7-C7H7)V(η5-C5H4-X-η5-C5H4)V(η7-C7H7)], Mediated by the spacers X=(Z)-CH=CH-, (E)-CH=CH-, >C=CH2, -CH2CH2, and -CH2-**[J]. Chem Eur J, 2005, 11(24): 7 427-7 439.

[29] Elschenbroich C, Lu F, Harms K, et al. Electrochemical behavior and EPR study of the paramagnetic termetallocene Di([5]trovacenyl-tetramethyl-η5-cyclopentandienyl)iron[J]. Polyhedron, 2014, 79: 300-305.

[30] Chaicharoenwimolkul L, Chairam S, Namkajorn M, et al. Effect of ferrocene substituents and ferricinium additive on the properties of polyaniline derivatives and catalytic activities of palladium-doped poly(m-ferrocenylaniline)-catalyzed suzuki-miyaura cross-coupling reactions[J]. J Appl Polym Sci, 2013, 130(3): 1 489-1 497.

[31] Souto M, Morales D C, Guasch J, et al. Intramolecular electron transfer and charge delocalization in bistable donor-acceptor systems based on perchlorotriphenylmethyl radicals linked to ferrocene and tetrathiafulvalene units[J]. J Phys Org Chem, 2014, 27(6): 465-469.

[32] Ratera I, Ruiz-Molina D, Wurst K, et al. A new photomagnetic molecular system based on photoinduced self-assembly of radicals[J]. Angew Chem Int Ed, 2001, 40(5): 919-922.

[33] Takai A, Yasuda T, Ishizuka T, et al. A directly linked ferrocene-naphthalenediimide conjugate: Precise control of stacking structures of π-systems by redox stimuli[J]. Angew Chem Int Ed, 2013, 52(35): 9 167-9 171.

[34] Iordache A, Oltean M, Milet A, et al. Redox control of rotary motions in ferrocene-based elemental ball bearings[J]. J Am Chem Soc, 2012, 134(5): 2 653-2 671.

[35] Erben M, Veselý D, Vinklárek J, et al. Acyl-substituted ferrocenes as driers for solvent-borne alkyd paints[J]. J Mol Catal A-Chem, 2012, 353, 354: 13-21.

[36] Schreckenbach G, Ziegler T. Density functional calculations of NMR chemical shifts and ESR g-tensors[J]. Theor Chem Acc, 1998, 99(2): 71-82.

[37] Bezuidenhout D I, van der Westhuizen B, Swarts P J, et al. Redox behaviour of cymantrene fischer carbene complexes in designing organometallic multi-tags[J]. Chem Eur J, 2014, 20(17): 4 974-4 985.

Outlines

/