A nano-scale triangular ring cluster of indium–selenide: the structure and templating effect

Abstract

Different from the dominating supertetrahedral structure of InSe clusters, co-assembled nano-scale In33Se60 triangular ring clusters and wheel-shaped In18Se30 clusters have been found. The unusual second-sphere coordination templating effect of the Mn(dach) complexes and the central Mn(2+) ion is responsible for the formation of the triangular ring. The optical and electronic properties are discussed.

Structural Chemistry of Giant Metal Based Supramolecules

“…216,217 A good illustration of a wheel-shaped cluster is the quite peculiar compound Mn 2 [Mn(dach) 3 ] 3 [Mn 9 In 33 Se 60 (dach) 24 ] 2 -[In 18 Se 30 (dach) 6 ](Hdach) 11 Cl 9 (dach = 1,2-diaminocyclohexane) reported by J. Dai (Soochow Univ., P. R. China). 218 Two types of wheel-shaped anionic clusters cocrystallize in this compound, the smaller, [In 18 Te 30 (dach) 6 ] 6− one with 2.3 nm in ø, and the larger one, [Mn 9 In 33 Se 60 (dach) 24 ] 3− with 2.8 nm in ø (Figure 28).…”

“…Strictly speaking, these compounds are rather mixed salts than cocrystals built up from different molecules. The examples of such "mixed salts" can be found among the metal clusters, 445 the metal chalcogenide clusters (Figure 28), 218 POMs, 446 or Cp R Fe(η 5 -P 5 )-based supramolecules. 371 However, true cocrystals do exist among supramolecules.…”

“…Figure 28. Two crystallographically unique anionic metal-chalcogenide clusters with (a) {In 18 Se 30 } and (b) {Mn 9 In 33 Se 60 } cores 218. …”

A wheel-shaped gallium-sulfide molecular ring with enhanced photocatalytic activity via indium alloying

“…56 The slow development of the molecular ring in CCMCs is probably due to the intrinsic tetrahedral coordination mode and inflexible Q–M–Q angle of the MQ 4 subunit (M = In/Ga/Sn/Ge, Q = S/Se/Te), 57,58 and compared with In–Te/Se and Ge–Se molecular rings, creating sulfide based nanorings is much more challenging due to the lower structural flexibility reflected by the relatively rigid S–M–S angle. 37,39…”

Unique Two-Dimensional Indium Telluride Templated by a Rare Wheel-Shaped Heterobimetallic Mn/In Cluster

“…A possible explanation may be the fact that Mn1 adopts an octahedral coordination geometry, while the remaining Mn 2+ cations appear in the crystal structure exhibiting distorted octahedral/tetrahedral coordination environments, which leads to a multitude of spin orientations. Upon cooling, the χ M T value of [Mn 4.78 In 2.22 (ea) 12 ] n [In 9.79 Mn 0.21 Te 17 ] n decreases gradually to 50 K and then decreases abruptly, reaching 4.74 cm 3 K mol –1 at 2 K, as a consequence of a strong antiferromagnetic coupling interaction between Mn 2+ ions. , The χ M –1 versus T of [Mn 4.78 In 2.22 (ea) 12 ] n [In 9.79 Mn 0.21 Te 17 ] n above 50 K can be fitted to the Curie–Weiss law χ M = C /( T – θ), which gives a Weiss constant of θ = −20.94 K. The negative θ value confirms the presence of an antiferromagnetic coupling interaction. The alternating-current (ac) susceptibilities did not exhibit any clear frequency dependence, even at low temperatures (Figure S5), indicating the absence of any long-range magnetic correlations between the Mn 2+ cations.…”