Magnetic Properties of One- and Two-Dimensional Functional Materials: Oxygen Molecules Encapsulated in Single-Walled Carbon Nanotubes and Copper Ions Embedded into Phthalocyanine Sheets
Authors: Hagiwara Masayuki , Kida Takanori , Matsuda Kazuyuki , Kyakuno Haruka , Maniwa Yutaka , Honda Zentaro , Sakaguchi Yuya , Tashiro Makoto , Sakai Masamichi , Fukuda Takeshi , Kamata Norihiko , Okunishi Kouichi 
Published: March 2019

Background:
In this paper, we report on the topics of one-dimensional (1D) and two-dimensional
(2D) functional materials. Single-Walled Carbon Nanotubes (SWCNTs) are seamless hollow cylinders made of
hexagonal lattice graphite sheets. The SWCNTs have attracted considerable attention due to the applicability of
their enclosed nanospaces to engineering, and many types of guest materials are encapsulated inside their 1D
space, expecting unusual properties. The poly Transition Metal (TM) phthalocyanine, in which phthalocyanine
units are extended in two dimensions by sharing benzene rings, is one of the examples of the TM containing 2D
carbon materials. Because of strong correlation between localized d-electrons in the TM atom and delocalized
π-electrons on the poly phthalocyanine frame, it is expected that spin-polarized conduction, which is useful for
the spintronic applications.

Objectives:
The objective of the first work is to synthesize SWCNTs encapsulating oxygen molecules having
spin one, whose O-O bond directions are aligned to the longitudinal direction of the SWCNTs. The objective of
the second work is to synthesize Poly Cu Phthalocyanine (PCuPc) through a bottom-up method by using copper
octacyanophthalocyanine as a building block and to elucidate its crystal structure and magnetic properties.

Methods:
SWCNTs with inner diameter of ca 0.8 nm were prepared by the CoMoCAT method, and encapsulated together with oxygen molecules (~400 Torr) into a high-purity quartz tube. To subtract the background signals of the SWCNTs and the quartz tube, we prepared the same SWCNTs inducing He gas after evacuating oxygen molecules. Magnetization measurements of these SWCNTs samples were conducted by means of a SQUID magnetometer and a pulse magnet using an induction method. PCuPc were synthesized by a solid state reaction of octacyanophthalocyanine, tetracyanobenzene, and CuCl2·2H2O in glass ampoules sealed after evacuation. The as-synthesized samples were characterized using XRD analysis and TEM microscopy. Magnetization measurement of the samples were done by using a SQUID magnetometer.

Results:
The intrinsic magnetization data from oxygen molecules inside the SWCNTs (temperature and magnetic field dependence) show magnetic properties typical of the spin-one Heisenberg antiferromagnet named a Haldane magnet. PCuPc and its half-filling counterpart were obtained by solid state reaction. Both magnetic susceptibility and magnetization of PCuPc are larger than those of half-filling PCuPc, but the magnitudes of the former sample are about 1.5 times larger than those of the latter one, which is expected to be twice from the geometric superlattice structure.

Conclusion:
We have studied magnetic properties (magnetic susceptibility and magnetization) of oxygen molecules encapsulated into Single Walled Carbon Nanotubes (SWCNTs) with diameters of about 0.8 nm, regarded as a 1D functional magnetic material, and Poly Copper Phthalocyanine (PCuPc) and poly half-filling copper phthalocyanine (half-filling PCuPc), regarded as 2D functional magnetic materials.