ABSTRACT
Exploring the reactions between atomically precise metal clusters and the consequences of such reactions has been an exciting field of research during the past decade. Initial studies in the area were on reactions between clusters in the solution phase, which proceed through the formation of dimers of reacting clusters. In the present work, we examine the interaction between two atomically precise clusters, [Au25(PET)18]- and [Ag25(DMBT)18]-, in the solid state, where PET and DMBT are 2-phenylethanethiol and 2,4-dimethylbenzenethiol, respectively. The experiments were performed using different ratios of these two clusters, and it was inferred that the kinetics of the reactions were faster compared with reactions in the solution. The metal exchange between these two clusters, due to their interactions in the solid state, leads to the formation of dimers, trimers, tetramers, and polymers of atomically precise alloy metal clusters. We observed polymer entities up to hexamers, which were observed for the first time. Control experiments revealed that metal exchange is a key factor leading to polymerization. Our work points to a new approach for synthesizing polymers of atomically precise alloy metal clusters.
ABSTRACT
The chemistry and physics of macropolyhedral B18H22 clusters have attracted significant attention due to the interesting photophysical properties of anti-B18H22 (blue emission, laser properties) and related potential applications. We have focused our attention on the "forgotten" syn-B18H22 isomer, which has received very little attention since its discovery compared to its anti-B18H22 isomer, presumably because numerous studies have reported this isomer as nonluminescent. In our study, we show that in crystalline form, syn-B18H22 exhibits blue fluorescence and becomes phosphorescent when substituted at various positions on the cluster, associated with peculiar microstructural-dependent effects. This work is a combined theoretical and experimental investigation that includes the synthesis, separation, structural characterization, and first elucidation of the photophysical properties of three different monothiol-substituted cluster isomers, [1-HS-syn-B18H21] 1, [3-HS-syn-B18H21] 3, and [4-HS-syn-B18H21] 4, of which isomers 1 and 4 have been proved to exist in two different polymorphic forms. All of these newly substituted macropolyhedral cluster derivatives (1, 3, and 4) have been fully characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, IR spectroscopy, and luminescence spectroscopy. This study also presents the first report on the mechanochromic shift in the luminescence of a borane cluster and generally enriches the area of rather rare boron-based luminescent materials. In addition, we present the first results proving that they are useful constituents of carbon-free self-assembled monolayers.
ABSTRACT
Correction for 'Secondary ligand-induced orthogonal self-assembly of silver nanoclusters into superstructures with enhanced NIR emission' by Korath Shivan Sugi, et al., Nanoscale, 2023, https://doi.org/10.1039/d3nr02561f.
ABSTRACT
Orthogonal self-assembly is one of the crucial strategies for forming complex and hierarchical structures in biological systems. However, creating such ordered complex structures using synthetic nanoparticles is a challenging task and requires a high degree of control over structure and multiple non-covalent interactions. In this context, nanoarchitectonics serves as an emerging tool to fabricate complex functional materials. Here, we present a secondary ligand-induced orthogonal self-assembly of atomically precise silver nanoclusters into complex superstructures. Specifically, we use Ag14NCs protected with naphthalene thiol and 1,6-bis(diphenylphosphino)hexane ligands. Controlled addition of 1,6-bis(diphenylphosphino)hexane, the secondary ligand resulted in a self-assembled supracolloidal structure including helical fibers, spheres, and nanosheets. The self-assembly process is tunable by controlling the molar ratio of the ligand. The resulting superstructures exhibit enhanced NIR emission due to restricted intramolecular motion. This demonstrates that by tuning supramolecular interactions, hierarchical nanostructures with desired properties similar to biomolecules can be obtained from atomically precise building blocks.
