Abstract
The interesting physical and chemical properties of carbon nanotubes (CNTs) have prompted the search for diverse inorganic nanotubes with different compositions to expand the number of available nanotechnology applications. Among these materials, crystalline inorganic nanotubes with well-defined structures and uniform sizes are suitable for understanding structure–activity relationships. However, their preparation comes with large synthetic challenges owing to their inherent complexity. Herein, we report the example of a crystalline nanotube array based on a supertetrahedral chalcogenide cluster, K3[K(Cu2Ge3Se9)(H2O)] (1). To the best of our knowledge, this nanotube array possesses the largest diameter of crystalline inorganic nanotubes reported to date and exhibits an excellent structure-dependent electric conductivity and an oriented photoconductive behavior. This work represents a significant breakthrough both in terms of the structure of cluster-based metal chalcogenides and in the conductivity of crystalline nanotube arrays (i.e., an enhancement of ~4 orders of magnitude).
Highlights
The interesting physical and chemical properties of carbon nanotubes (CNTs) have prompted the search for diverse inorganic nanotubes with different compositions to expand the number of available nanotechnology applications
Compared with atomic-layered single-wall nanotubes (Fig. 1c), the crystalline inorganic nanotube arrays assembled by clusters could possess greater numbers of exposed sites or external surfaces due to the significantly more rugged surface constructed by protruding clusters (Fig. 1d); this could result in interesting properties
We report the preparation of a supertetrahedral chalcogenide-cluster-based compound {K3[K(Cu2Ge3Se9)(H2O)}] (1), featuring a 1D nanotubular structure, and examination of its oriented photoconductive property. We expect that this structure will be distinct from the traditional 0D discrete clusters, 1D chains, 2D layers, and 3D frameworks constructed by supertetrahedral chalcogenide clusters during the past 50 years[28,29,30] and that it will constitute another significant breakthrough in the field of supertetrahedral clusters since the emergence of the supertetrahedral [Na4Ge4S10] T2 cluster (“T” denotes tetrahedral, two denotes the number of Ge sites along the tetrahedron edge) in 197128,31–35
Summary
The interesting physical and chemical properties of carbon nanotubes (CNTs) have prompted the search for diverse inorganic nanotubes with different compositions to expand the number of available nanotechnology applications Among these materials, crystalline inorganic nanotubes with well-defined structures and uniform sizes are suitable for understanding structure–activity relationships. High-quality nanotubes, synthesized using a bottom-up strategy and possessing an atomically precise structure and uniform size, are highly desirable for understanding structure–property relationships and future applications[7,20] This type of nanotube is often negatively charged and can be assembled into crystal arrays by ionic or other weak interactions (Fig. 1b), thereby providing a platform for studying ion transportation and ionic conduction within or outside the nanotubes;[6,7,17] this is important in the context of nanoelectronics and biotechnology[26]. We expect that this structure will be distinct from the traditional 0D discrete clusters, 1D chains, 2D layers, and 3D frameworks constructed by supertetrahedral chalcogenide clusters during the past 50 years[28,29,30] and that it will constitute another significant breakthrough in the field of supertetrahedral clusters since the emergence of the supertetrahedral [Na4Ge4S10] T2 cluster (“T” denotes tetrahedral, two denotes the number of Ge sites along the tetrahedron edge) in 197128,31–35
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