Arrays of Chiral Nanotubes and a Layered Coordination Polymer Containing Gallium–Sulfide Supertetrahedral Clusters

Abstract

Organically functionalised supertetrahedral clusters: Two novel coordination polymers, consisting of chiral helical nanotubes and of composite layers, have been obtained by linkage of gallium-sulfide supertetrahedral clusters and dipyridyl ligands (see picture).

Three‐Dimensional Covalent Co‐Assembly between Inorganic Supertetrahedral Clusters and Imidazolates

“…[12] Recently, further progress has led to 1D and 2D assembly of inorganic Ga-S supertetrahedral clusters. [4,13] Despite these promising advances, a number of limitations still existed prior to this work, including: 1) only neutral organic ligands (usually bipyridine types) have been shown to function as cross-linkers between tetrahedral clusters; 2) only low-dimensional (0D, 1D, and 2D) superlattices have been made; and 3) for supertetrahedral clusters, the size of the cluster is limited to T3 with 10 metal sites. [4] In this work, we seek to explore a new type of chemistry at the interface of two seemingly unrelated types of materials: 1) inorganic chalcogenide clusters and frameworks (e.g., CdInS-44-[Cd 4 In 16 S 33 ] 10À , UCR-17-[Cu 5 In 30 S 54 ] 13À ), and 2) zeolitic imidazolate frameworks, commonly called ZIFs (e.g., [Zn(2-methylimidazolate) 2 ]).…”

“…While 3D frameworks comprising only supertetrahedral clusters are well known, [5,9,11] all previous efforts to cross-link tetrahedral chalcogenide clusters of any composition (e.g., organic-capped Cd-S-SPh system or inorganic Ga-S system) with organic ligands have only resulted in formation of low-dimensional structures (up to 2D). [13] Formation of SCIFs depends on achieving a suitable balance among a number of factors. The complexity of the assembly can be seen from T4-containing SCIF-8 and SCIF-9 which require the assembly of a number of individual solution species (In 3+ , Cd 2+ , S 2À , IM À , plus extra-framework charge-balancing and porefilling species such as HDBU + ), each of which plays a unique role.…”

A Porous Flexible Homochiral SrSi2 Array of Single‐Stranded Helical Nanotubes Exhibiting Single‐Crystal‐to‐Single‐Crystal Oxidation Transformation

“…[13] A parallel association of octuple helices has been shown by Wang et al to form a 3D chiral network of nanotubes with openings of 19.4 by 22.4 . [14] Chiral nanotubes with negligible porosity (< 2 inner diameter) formed by quadruple-stranded helices were recently reported by Vaquerio et al [15] In contrast to these examples, a single helix spiraling with a short pitch (width of one complete helix turn) can form hollow tubular structures with uniform, fixed internal diameters. Two exceptional examples of single-stranded helical metal-organic nanotubes have been presented in the literature: a dense homochiral array of nanotubes originating from nine-fold interlocking helices, [16] and a chiral nanotube formed from the helical assembly of alternating p-sulfonatocalix [4]arenas and lanthanide ions.…”

A Porous Flexible Homochiral SrSi2 Array of Single‐Stranded Helical Nanotubes Exhibiting Single‐Crystal‐to‐Single‐Crystal Oxidation Transformation

“…to form a 3D chiral network of nanotubes with openings of 19.4 Å by 22.4 Å 14. Chiral nanotubes with negligible porosity (<2 Å inner diameter) formed by quadruple‐stranded helices were recently reported by Vaquerio et al 15. In contrast to these examples, a single helix spiraling with a short pitch (width of one complete helix turn) can form hollow tubular structures with uniform, fixed internal diameters.…”