# Observation and Characterization of Fragile Organometallic Molecules Encapsulated in Single-Wall Carbon Nanotubes

Authors: Daisuke Ogawa; Ryo Kitaura; Takeshi Saito; Shinobu Aoyagi; Eiji Nishibori; Makoto Sakata; Tetsuya Nakamura; Hisanori Shinohara
Journal: Journal of Nanomaterials
 (2014)

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## Abstract

Thermally fragile tris(η
5-cyclopentadienyl)erbium (ErCp3) molecules are encapsulated in single-wall carbon nanotubes (SWCNTs) with high yield. We realized the encapsulation of ErCp3 with high filling ratio by using high quality SWCNTs at an optimized temperature under higher vacuum. Structure determination based on high-resolution transmission electron microscope observations together with the image simulations reveals the presence of almost free rotation of each ErCp3 molecule in SWCNTs. The encapsulation is also confirmed by X-ray diffraction. Trivalent character of Er ions (i.e., Er3+) is confirmed by X-ray absorption spectrum.


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## Body

## 1. Introduction

Nanowires with a few atoms in diameter show completely different properties from those of the three-dimensional bulk materials [1–11]. However, in general, those ultimately thin nanowires are unstable under atmospheric conditions and they are therefore quite difficult to realize.In 1998, it was found that single-wall carbon nanotubes (SWCNTs) are able to encapsulate C60 fullerenes in their inner hollow space [12]. Since the discovery, various materials have been encapsulated in SWCNTs, which has produced a wide variety of low-dimensional hybrid nanomaterials; SWCNTs have provided ideal nanospace and protective walls for encapsulated materials [13–17]. In addition to their specific structure, these newly formed hybrid nanomaterials have shown interesting properties [18–20].The encapsulation of organometallic complex molecules, such as Co(C5H5)2 [21] and Fe(C5H5)2 [22–25], in the SWCNTs has attracted wide attention due to an expected control of SWCNT’s electronic properties through charge transfer between encapsulates and SWCNT. Furthermore, organometallics can act as a precursor to form metal atomic wires in SWCNTs via the so-called nanotemplate reaction, which may lead to the formation of novel metal atomic wires.Encapsulation of organometallics in SWCNTs, however, has so far been difficult, mainly because of the fact that, under atmospheric condition or at high temperature, such materials normally decompose during the encapsulation process. Here, we have focused on the development of a versatile method to encapsulate fragile organometallic complexes in SWCNTs. To confirm the encapsulation, we have employed a structure determination procedure that is based on high-resolution transmission electron microscope (HR-TEM) observations and HR-TEM image simulation by the multislice method [26].


## 2. Experimental

SWCNTs were synthesized by the so-called extended direct injection pyrolytic synthesis (e-DIPS) [27]. As-produced e-DIPS SWCNTs (a-CNTs) were annealed at 1200°C in vacuum (~10−5Pa) for 14 hours in order to remove remaining Fe catalyst nanoparticles and amorphous carbon impurities [28]. Before the encapsulation reaction, the purified e-DIPS SWCNTs (p-CNTs) were heated under dry air flow at 600°C for 30 min in order to open the endcap of SWCNTs.ErCp3 is an air- and moisture-sensitive material and decomposes easily upon exposure to the atmosphere [29]. ErCp3 was thus carefully handled and purified by sublimation at 200°C under high vacuum (~10−4 Pa) [29] and was kept in an anaerobic glove box. In the following experiments, all the sample preparation was performed using the purified ErCp3 under anaerobic condition to avoid any undesired degradation of ErCp3 during the preparation. Open-ended p-CNTs (o-CNTs) were vacuum sealed (~10−4 Pa) in a Pyrex tube with the purified ErCp3, and the sealed Pyrex tube was heated at 250°C for 72 hours. At this temperature and pressure, ErCp3 was sublimed and encapsulated in the hollow space of the SWCNTs. The as-prepared ErCp3@o-CNTs were washed with anhydrous tetrahydrofuran in order to remove any ErCp3 molecules physically adsorbed on the outer surface of the SWCNTs. The final products were dried at 80°C for 12 hours. As a control experiment, we also prepared a sample, ErCp3@p-CNTs, by performing the encapsulation process of ErCp3 on p-CNTs.


## 3. Results and Discussion

Figure1 shows a thermal gravimetric analysis (TGA) trace of a-CNTs and p-CNTs. Two shoulders were clearly seen at around 400°C and 600°C on the TGA curve of a-CNTs. The former and the latter shoulders correspond to the oxidation of amorphous carbon and the oxidation of SWCNTs and graphite, respectively. In contrast, only one sharp drop at 500°C and a smaller amount of residual material (3.84 wt.%) were observed in the TGA curve of p-CNTs, which indicates higher purity of p-CNTs than that of a-CNTs.Figure 1
TGA profiles of as-produced and purified e-DIPS SWCNT. The sharp drop in sample weight at higher temperature and the smaller amount of residual material show higher quality of purified SWCNTs than that of as-produced ones.Figures2(a) and 2(b) are HR-TEM images of a-CNTs and p-CNTs, respectively. As seen in Figure 2(a), dark contrasts of Fe catalyst nanoparticles and amorphous impurity attached outer surface of SWCNTs are clearly observed. The amount of Fe catalyst nanoparticles and amorphous impurity greatly decreases after purification, as shown in Figure 2(b). In Figures S1(a) and (b) (see Figures S1(a) and S1(b) in Supplementary Material available online at http://dx.doi.org/10.1155/2014/539295), the corresponding energy dispersive X-ray (EDX) spectra are shown. Obtained spectra clearly show that the amount of residual Fe had been greatly reduced by purification. These HR-TEM images are consistent with the TGA results.HR-TEM image of (a) as-produced and (b) purified e-DIPS SWCNTs.
(a)
(b)Figures3(a) and 3(b) show HR-TEM images of ErCp3@o-CNTs having different tube diameters. As seen in Figure 3(a), dot-like contrasts align in one-dimensional fashion at intervals of 0.94 nm inside SWCNTs whose diameter is 1.30 nm. The observed interval of 0.94 nm is almost the same with the molecular size of the ErCp3 molecule; the molecular size was estimated considering van der Waals radius of constituent atoms. Moreover, the difference between the diameter of SWCNTs (i.e., 1.30 nm) and the intervals of dot-like contrasts (i.e., 0.94 nm) observed is nearly equal to the van der Waals radii of the inner wall of SWCNTs (~0.34 nm) [30, 31].HR-TEM images of ErCp3 molecules in (a) thinner and (b) broader SWCNTs. The inset of (a) is a simulated HR-TEM image of ErCp3@o-CNT.
(a)
(b)When the diameter of SWCNTs is larger than 1.30 nm, ErCp3 molecules aggregate to form clusters (Figure 3(b)). An EDX spectrum observed in the same area shows strong peaks that can be attributed to Er M
α, L
α, and L
β (Figure S1(c)). The dark spots were not observed in o-CNTs prior to the ErCp3 encapsulation, and no EDX peaks from Er atoms were observed. Therefore, we conclude that observed contrasts arise from encapsulated ErCp3 molecules forming one-dimensional regular array in hollow space of SWCNTs. The estimated filling ratio from the HR-TEM images is ca. 30% or more, which is substantially higher than that previously reported for organometallic complexes molecules encapsulated in SWCNTs [21, 22].To confirm the high filling ratio of ErCp3 in o-CNTs, we have measured X-ray diffraction (XRD) patterns. Figures S2(a) and (b) show the XRD patterns of o-CNTs, ErCp3@o-CNTs, p-CNTs, and ErCp3@p-CNTs. As shown in Figures S2(a) and (b), the number of diffraction peaks is limited, so that it is difficult to determine precise filling ratio by pattern fitting. Filling of ErCp3 molecules, however, can be confirmed by changes in intensity of (10) peak. As clearly seen in Figure S2(a), the intensity of (10) peak of ErCp3@o-CNTs is much smaller than that of o-CNTs. This is a clear indication that the inner space of o-CNTs is filled with guest materials (i.e., ErCp3) [14, 32, 33].The intensity of (10) peak of ErCp3@p-CNTs is comparable to that of p-CNTs, suggesting that the observed intensity drop in ErCp3@o-CNTs can be attributed to encapsulation of ErCp3 molecules (Figure S2(b)). The high filling ratio is caused by (1) purification and anaerobic handling of ErCp3, (2) an improved preparation method of o-CNTs (i.e., high quality, proper diameter, and optimized cap-opening conditions), and (3) performing the encapsulation reaction under high vacuum at optimized conditions.Based on the observed HR-TEM images of ErCp3@SWCNT, we have constructed a structure model. Image simulations by the multislice method (at a defocus of 600, 650, 700, 750, and 800 nm) have been carried out based on the structure model constructed. To attain satisfactory agreements between the observed and simulated HR-TEM images, we have superimposed simulated HR-TEM images of ErCp3@SWCNT with different molecular orientations, in which simulated images based on fixed molecular orientations do not match with the observed images.As illustrated in inset of Figure3(a), the final simulated HR-TEM image well reproduces both the observed dark ellipsoids and their intensities. Hence, encapsulated ErCp3 molecules may be rotating much faster than the time scale of HR-TEM observation (the typical exposure time is several seconds). This suggests that the interaction between encapsulated ErCp3 and SWCNTs should fairly be weak. Since the ionization energy of ErCp3 (7~8 eV) is much larger than the threshold under which charge transfer interaction between SWCNTs occurs [14]; the interaction between ErCp3 and SWCNTs should not be significant. Here the ionization energy of ErCp3 was estimated from the ionization energy of other molecules, that is, LaCp3 (7.9 eV), PrCp3 (7.68 eV), and TmCp3 (7.43 eV), respectively [34].To further investigate the electronic structure of ErCp3, X-ray absorption spectrum (XAS) measurements at the Er M
5 absorption edge were performed, which indicates trivalency of Er ions (i.e., Er3+) (Figure 4). The spectrum is almost identical to that of Er2O3, suggesting that encapsulated ErCp3 molecules do not transform into any clusters or aggregates as such. SWCNTs act only as a template that restricts the space where ErCp3 molecules are encapsulated. The restricted space of SWCNTs is, therefore, well suited to stabilize unstable metal-containing complexes and to create low-dimensional alignment of various metal complexes including unstable organometallics.Figure 4
X-ray absorption spectra of ErCp3@o-CNTs and Er2O3, confirming the presence of Er3+ in both species.


## 4. Conclusions

We have successfully fabricated novel low-dimensional crystalline ErCp3 nanowires encapsulated in SWCNTs with filling yield of ~30% and characterized their structural properties. Encapsulation reactions carried out under high temperature and high vacuum conditions using high quality SWCNTs are necessary in order to obtain ErCp3@SWCNTs. A structure determination method based on the simulated annealing method and HR-TEM image simulation has been shown to be useful in characterizing the crystal structure of metal complex nanowires formed in SWCNTs. The present study may lead to future fabrication of various low-dimensional metal complexes in SWCNTs in high yield.



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*Source: 539295-2014-06-09.xml*