Dmitri V.
Konarev
*a,
Sergey I.
Troyanov
b,
Akihiro
Otsuka
c,
Hideki
Yamochi
c,
Gunzi
Saito
de and
Rimma N.
Lyubovskaya
a
aInstitute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432 Russia. E-mail: konarev3@yandex.ru
bChemistry Department, Moscow State University, Leninskie Gory, 119991 Moscow, Russia
cResearch Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
dFaculty of Agriculture, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku, Nagoya 468-8502, Japan
eToyota Physical and Chemical Research Institute, 41-1, Yokomichi, Nagakute, Aichi 480-1192, Japan
First published on 19th February 2016
The reduction of CoII(dppe)Cl2 with sodium fluorenone ketyl produces a red solution containing the CoI species. The dissolution of C60 in the obtained solution followed by the precipitation of crystals with hexane yields a salt {CoI(dppe)2+}(C60˙−)·2C6H4Cl2 and a novel complex {Co(dppe)2Cl}(C60) (1). With C70, only the crystals of {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 (2) are formed. Complex 1 contains zig-zag fullerene chains whereas closely packed double chains are formed from fullerenes in 2. According to the optical spectra and magnetic data charge transfer occurs in both 1 and 2 with the formation of the CoII(dppe)2Cl+ cations and the C60˙− or C70˙− radical anions. In spite of the close packing in crystals, C60˙− or C70˙− retain their monomeric form at least down to 100 K. The effective magnetic moments of 1 and 2 of 1.98 and 2.27μB at 300 K, respectively, do not attain the value of 2.45μB expected for the system with two non-interacting S = 1/2 spins at full charge transfer to fullerenes. Most probably diamagnetic {CoI(dppe)2Cl}0 and neutral fullerenes are partially preserved in the samples which can explain the weak magnetic coupling of spins and the absence of fullerene dimerization in both complexes. The EPR spectra of 1 and 2 show asymmetric signals approximated by several lines with g-factors ranging from 2.0009 to 2.3325. These signals originate from the exchange interaction between the paramagnetic CoII(dppe)2Cl+ cations and the fullerene˙− radical anions.
In our previous work we studied coordination compounds of fullerene C60 with cobalt in zero oxidation state containing Ph3P and diphosphine ligands (including 1,2-bis(diphenylphosphino)ethane, dppe) and in some cases benzonitrile.14–16 In this work we studied the interaction of fullerenes C60 and C70 with Co(dppe)2Cl prepared by the reduction of CoII(dppe)Cl2 with sodium fluorenone ketyl. Crystalline {Co(dppe)2Cl}(C60) (1) and {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 (2) compounds were obtained together with the previously studied salt {CoI(dppe)2+}(C60˙−)·2C6H4Cl2.12 We present crystal structures, and optical and magnetic properties of these complexes. Compound 2 is a rare example of an ionic fullerene structure containing monomeric C70˙− radical anions while they form single-bonded (C70−)2 dimers17–19 in most of the anion radical salts.
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Scheme 1 Redox potentials of the components used in the synthesis of Co(dppe)-fullerene complexes. All potentials are given vs. SCE. |
Sodium fluorenone ketyl (fluorenone˙−)(Na+) is a stronger reducing agent than TDAE (Scheme 1) with the first oxidation potential of about −1.30 V vs. Ag/AgCl or (−1.255 V vs. SCE).23 Therefore, this ketyl can also reduce CoII(dppe)Cl2 to generate the CoI species. Potentially it can also reduce CoII(dppe)Cl2 to the Co0 species but such a redox process is hindered in nonpolar o-dichlorobenzene.
In this study, the formation of CoI species was detected by the color change of the reaction mixture from the green color of CoII(dppe)Cl2 to red during the reduction with sodium fluorenone ketyl. After the removal of unreacted sodium fluorenone ketyl by filtration, the generated CoI(dppe)n+ (n = 1, 2) was treated with neutral fullerenes. CoI(dppe)2Cl is rather a strong donor and potentially it can reduce fullerenes providing the CT complexes composed of CoII(dppe)22+ and C60˙− or C70˙− radical anions. While the main product of this reaction was {Co(dppe)2Cl}(C60) (1), the {CoI(dppe)2+}(C60˙−)·2C6H4Cl2 salt12 is also crystallized in 20% yield. The {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 (2) complex crystallized exclusively with C70.
The UV-visible-NIR spectra of 1 and 2 are shown in Fig. 1. The absorption bands in the spectrum of 1 at 38000, 29700 cm−1 (262, 334 nm) and the weaker band at 16860 cm−1 (612 nm) can be attributed to C60 whereas the bands in the NIR range at 10
650 and 9240 cm−1 (948, 1087 nm) (Fig. 1a) show the presence of C60˙−.5,6 The broad low-energy band of relatively weak intensity at about 7660 cm−1 (1300 nm) (Fig. 1a) can be ascribed to the CT transition between fullerenes or the Co(dppe)2Cl and fullerene species. Similarly, absorption bands in the spectrum of 2 at 26
000 and 20
840 cm−1 (382 and 480 nm) are ascribed to C70. The broad absorption band in the NIR range can be reproduced by two Gaussian curves with maxima at about 9900 and 7500 cm−1 (1010 and 1330 nm, Fig. 1b and 2). The position of the latter band is close to that in the solution spectrum of monomeric C70˙−.5,6,26 It should be noted that generally C70 monoanions form singly bonded (C70−)2 dimers in solids to show two bands in the NIR range at about 11
360 and 8200 cm−1 (880 and 1220 nm, Fig. 2).17–19 The strong shift of the (C70−)2 band at 880 nm to 1010 nm in the spectrum of 2 proves the failure of dimer formation in 2. So far, monomeric C70˙− are preserved only in the (Ph4P+)2(C70˙−)(I−) salt due to the long distances between fullerenes.27 The broad band at about 9900 cm−1 (1010 nm) can be attributed to the CT between fullerenes or the Co(dppe)2Cl and the fullerene species. Low energy CT bands (ca. 2000–5000 cm−1) which correspond to the Drude type reflectivity spectra characteristic of metals are not observed in the spectra of both 1 and 2.
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Fig. 1 Spectra of 1 (a) and 2 (b) in the UV-visible-NIR range measured at room temperature using KBr pellets prepared under anaerobic conditions. |
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Fig. 2 The comparison of visible-NIR spectra of the C70˙− radical anions in 2 (upper spectrum) and the (C70−)2 dimers in the complex (Cp2Co+)2(C70−)2·2C6H4Cl2 (lower spectrum).8 |
Each Co(dppe)2Cl unit is surrounded by four C60 cages (Fig. 3c). Nearly spherical C60 is inserted into the cavities formed by four phenyl substituents of Co(dppe)2Cl, and multiple vdW C,H(Co(dppe)2Cl)⋯C(C60) contacts are formed. One of the four surrounding fullerenes forms short Cl(Co(dppe)2Cl)⋯C(C60) contacts of the 2.998–3.107 Å length. The shortest distances (5.22–5.41 Å) between cobalt and the C60 carbon atoms are attained with the fullerene closest to the chloride anion of Co(dppe)2Cl.
Fullerenes C70 form closely packed double chains arranged along the a axis in {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 (2). The longer axis of C70 is directed along this axis, and the ctc interfullerene distance is 10.81 Å in this direction. The ctc interfullerene distance in the double chains along the b axis is 10.18 Å. As a result, multiple short vdW C⋯C contacts are formed between fullerenes (shown with green dashed lines in Fig. 4a). Double fullerene chains are completely isolated to give the ctc interfullerene distances among the neighboring double chains longer than 14 Å (Fig. 4b). Each Co(dppe)2Cl unit is surrounded by four C70 cages in 2 (Fig. 4c). In this case phenyl substituents cannot form a suitable cavity for a larger C70 ellipsoid, and it is positioned asymmetrically to Co(dppe)2Cl (Fig. 4c). There are no short Cl(Co(dppe)2Cl)⋯C(C70) contacts in 2 unlike the crystal structure of 1. The shortest Co⋯C(C70) distances are 5.94–6.70 Å.
The arrangement of ligands around cobalt atoms in the Co(dppe)2Cl units is similar in 1 and 2. However, these units have different bond lengths at the cobalt atoms. The cobalt atoms are located in the pyramidal environment in both the units formed by four phosphorus atoms and one chloride anion. The Co atoms are not located strictly in the plane of four phosphorus atoms but move out of this plane by 0.110 and 0.124 Å towards chloride anion in 1 and 2, respectively. The dimension of pyramidal coordination is informative to evaluate the charge on Co. As listed in Table 1, the average of Co–P length is increased according to the charge on Co (see, #0, 3–5).
Compound | Co–Cl | Co–P (average) | Ref. | |
---|---|---|---|---|
#0 | {CoI(dppe)2}+(C60˙−)·2C6H4Cl2 (almost square planar) | 2.193(2) | 12 | |
#1 | {Co(dppe)2Cl}(C60) (1) | 2.366(2) | 2.2495(8) | This work |
#2 | {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 (2) | 2.403(3) | 2.2725(8) | This work |
#3 | {CoII(dppe)2Cl}+(SnCl3−)·C6H5Cl | 2.398(2) | 2.275(2) | 28 |
#4 | {CoII(dppe)2I}+(I−)·CHCl3 | 2.283(3) | 29 | |
#5 | {CoII(dppe)2(CH3CN)}2+ (BF4−)2·C3H6O | 2.306(3) | 21 |
The value of 2.2725(8) Å for 2 proves that Co is oxidized in this complex to almost +2, which corresponds well to a similar Co–Cl length to that of #3. On the contrary, the average Co–P length in 1 is shortened compared to those in CoII materials.
Compared with that in #0, the Co in 1 is regarded not to be oxidized fully to +2. This evaluation corresponds well to the optical spectra and magnetic data for 1.
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Fig. 5 Temperature dependencies for effective magnetic moments of 1 (a) and 2 (b), and reciprocal molar magnetic susceptibility of 1 (c) and 2 (d). |
Complex 1 manifests an intense asymmetric EPR signal at room temperature which can be fitted well by three components with g1 = 2.0968 (the linewidth (ΔH) of 15.51 mT), g2 = 2.0488 and ΔH = 11.06 mT and g3 = 2.0085 and ΔH = 8.16 mT (Fig. 6a). The starting CoI has S = 1 or most probably S = 0 spin state. Compounds of CoI with the S = 1 spin state can manifest triplet EPR signals, for example, CoI(Ph3P)3X (X = Cl, Br),31 but these signals cannot be observed by X-band EPR spectroscopy. Only high-frequency and -field EPR spectroscopy can be used for these purposes. Neutral fullerenes are EPR silent. Therefore, only the paramagnetic CoII(dppe)2Cl+ and the C60˙− or C70˙− radical anions can contribute to the EPR signals of 1 and 2. Here, it is noted that the spin susceptibility estimated by the EPR signal intensity showed the same temperature dependency as that of magnetic susceptibility determined by the SQUID technique both for 1 and 2. This means that there is no contribution of CoI to the magnetism in these materials.
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Fig. 6 (a) EPR signal for polycrystalline 1 at 305 K; temperature dependence of components of the EPR signal: (b) g-factor, (c) linewidth. |
CoII(dppe)Br2 shows the Lorentzian EPR signal with g = 2.0357 and ΔH = 15.5 mT. However, CoII(dppe)Br2 has tetrahedral geometry while the CoII(dppe)2Cl+ cations have the pyramidal environment for the cobalt atoms. Essential modification of the cobalt environment in the formation of CoII(dppe)2Cl+ can affect the EPR signal by shifting g-factors to higher values in comparison with that of CoII(dppe)Br2. The signals with a g-factor closer to that of C60˙− are also observed (g2 = 2.0488 and g3 = 2.0085) together with the signals characteristic of CoII. These signals could be ascribed to both CoII(dppe)2Cl+ and C60˙− species having exchange interaction. They are strongly narrowed with the temperature decrease (Fig. 6c) and grow in intensity with the temperature increase above 220 K. We attribute such behavior to the increase of the CT degree from Co(dppe)2Cl to C60. The component with g3 = 2.0980 splits into two components below 40 K positioned at g = 2.0979 and 2.1501. Both components shift to higher g-factors with the temperature decrease (Fig. 6b).
Complex 2 shows an intense EPR signal at room temperature which can be fitted by three Lorentzian lines with g1 = 2.3325 (ΔH = 5.62 mT), g2 = 2.2649 (ΔH = 9.20 mT), and g3 = 2.1428 (ΔH = 24.84 mT) (Fig. 7). The broad g3-component splits into two lines below 220 K which are positioned at g = 2.1829 (ΔH = 13.86 mT) and 2.0711 (ΔH = 25.64 mT) at 220 K. Spectrum of 2 contains also weak narrow signal with g = 2.0021 (ΔH = 0.28 mT) (Fig. 7a) which can appear due to air oxidation of fullerene anions. It is seen that the EPR signal in 2 is broader and has essentially higher g-factors of the lines in comparison with those of 1. We can suppose that lines in the EPR spectrum of 2 with lower g-factors of 2.18 and 2.07 have essential contribution from C70˙−. It is known that the C70˙− radical anions in (Ph4P+)2(C70˙−)(I−) show a broad EPR signal with a g-factor of 2.0047 (ΔH = 60 mT) at 300 K.27 Therefore, the lines in the spectrum of 2 originating from both CoII(dppe)2Cl+ and C70˙− are essentially broader and shifted to higher g-factors in comparison with those of 1. Lines with lower g-factors (g = 2.18 and 2.07) slightly grow in intensity with the temperature increase above 150 K and that can also be explained by the increase of the CT degree from Co(dppe)2Cl to C70.
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Fig. 7 EPR signal for polycrystalline 2 at 220 K (a); temperature dependence of the g-factor (b) and linewidth (c) of the components of the EPR signal of 2. |
The crystals of {Co(dppe)2Cl}(C60) (1) and {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 (2) were obtained by the following procedure. The reduction of green CoII(dppe)Cl2 (22 mg, 0.042 mmol) in 16 ml of C6H4Cl2 with sodium fluorenone ketyl (20 mg, 0.098 mmol) for 2 hours at 100 °C yielded a clear red solution. The solution was cooled down to room temperature and filtered into a flask containing fullerene C60 (30 mg, 0.042 mmol) for preparation of 1 and fullerene C70 (35 mg, 0.042 mmol) for preparation of 2. Fullerenes were dissolved in the obtained solution over 4 hours at 80 °C to produce violet-red and red solutions, respectively. After cooling down to room temperature the solutions were filtered into the tube for diffusion. The crystals of {Co(dppe)2Cl}(C60) (1) were obtained as black plates in 26% yield together with black elongated parallelepipeds of the previously reported salt {CoI(dppe)2+}(C60˙−)·2C6H4Cl212 (yield is 20%) which was identified by X-ray diffraction on several parallelepiped-shaped single crystals. The crystals of two phases have different shapes and were separated under a microscope in the glove box. The purity of 1 was supported by the absence of the line at g = 1.9986 (ΔH = 4.57 mT) characteristic of {CoI(dppe)2+}(C60˙−)·2C6H4Cl2. The crystals of {Co(dppe)2Cl}(C70)·0.5C6H4Cl2 (2) were obtained as black plates in 42% yield. Testing of several crystals from the synthesis shows the presence of only one phase in this synthesis.
Crystal data of 1 at 100(2) K: C112H48ClCoP4, Mr = 1611.76 g mol−1, black plate, monoclinic, C2/c, a = 22.1120(6), b = 19.1090(6), c = 17.0090(4) Å, β = 107.480(2)°, V = 6855.1(3) Å3, Z = 4, dcalc = 1.562 g cm−3, μ = 0.446 mm−1, F(000) = 3296, 2θmax = 58.4°, reflections measured 36820, unique reflections 9002, reflections with I > 2σ(I) = 6591, parameters refined 630, restraints 180, R1 = 0.0735, wR2 = 0.1851, G.O.F. = 1.083. The C60 cage is disordered over two orientations linked by a two-fold axis. CCDC 1437134.
Crystal data of 2 at 100(2) K: C125H50Cl2CoP4, Mr = 1805.36 g mol−1, black plate, monoclinic, P21/n, a = 10.8104(3), b = 39.8917(10), c = 18.2142(5) Å, β = 100.133(2)°, V = 7732.3(4) Å3, Z = 4, dcalc = 1.551 g cm−3, μ = 0.438 mm−1, F(000) = 3684, max. 2θmax = 53.5°, reflections measured 47143, unique reflections 15
869, reflections with I > 2σ(I) = 10
991, parameters refined 821, restraints 24, R1 = 0.0814, wR2 = 0.2035, G.O.F. = 1.000. The C70 cage is disordered between three orientations with the 0.45/0.30/0.25 occupancies. The solvent C6H4Cl2 molecule is statistically disordered between two orientations. CCDC 1437135.
Footnote |
† Electronic supplementary information (ESI) available: IR spectra of 1 and 2. CCDC 1437134 and 1437135. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5dt04627k |
This journal is © The Royal Society of Chemistry 2016 |