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Exploring the Geometric Space of Metal-Organic Polyhedrons (MOPs) of Metal-Oxo Clusters.

ABSTRACT: Metal organic polyhedra (MOPs) such as coordination cages and clusters are increasingly utilized across many fields, but their geometrically selective assembly during synthesis is nontrivial. When ligand coordination along these polyhedral edges is arranged in an unsymmetrical mode or the bridging ligand itself is nonsymmetric, a vast combinatorial space of potential isomers exists complicating formation and isolation. Here we describe two generalizable combinatorial methodologies to explore the geometrical space and enumerate the configurational isomers of MOPs with discrimination of the chiral and achiral structures. The methodology has been applied to the case of the octahedron {Bi₆Fe₁₃L₁₂} which has unsymmetrical coordination of a carboxylate ligand (L) along its edges. For these polyhedra, the enumeration methodology revealed 186 distinct isomers, including 74 chiral pairs and 38 achiral. To explore the programming of these, we then used a range of ligands to synthesize several configurational isomers. Our analysis demonstrates that ligand halo-substituents influence isomer symmetry and suggests that more symmetric halo-substituted ligands counterintuitively yield lower symmetry isomers. We performed mass spectrometry studies of these {Bi₆Fe₁₃L₁₂} clusters to evaluate their stability and aggregation behavior in solution and the gas phase showing that various isomers have different levels of aggregation in solution.

SUBMITTER: Kandasamy B

PROVIDER: S-EPMC8493551 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Polyhedrons, spheroids and bolas (PSBs) are present in lithic series from the Lower Palaeolithic onwards and are found in several regions of the world. Nevertheless, very little is known about them. We propose here to summarise, illustrate and discuss the current state of our knowledge about these artefacts. Based on the available data in the literature and on our observations of several collections, we set up a database comprising 169 Palaeolithic assemblages with PSBs. Thanks to the statistical analysis of these data, we aim to highlight potential relationships between PSB characteristics (e.g., quantity, raw material) and assemblage composition and context, according to regions and chrono-cultural attributions. We also aim to discuss the question of artefacts from possible independent local histories, especially in Northwest Europe, where these objects are scarce. Our study concludes that hard stones (stones with high resistance to a physical constraint) available locally were generally selected to produce PSBs. Soft sedimentary rocks are suitable for their manufacture, and were selected too, whereas siliceous materials were left aside. We hypothesise that the scarcity of PSBs in Northwest Europe could result from a combination of cultural and environmental factors: it could be part of a regional tradition, influenced by the abundance of siliceous materials in the environment. In this region where the lithic production is widely made of flint, even though other materials were available, objects made from hard stones are scarce, resulting in a toolkit with only rare PSBs and cleavers. Was flint too brittle for the functions of PSBs? Raw materials of PSBs are often similar to those of heavy-duty tools in assemblages, which could provide other clues about their functions (e.g., tasks requiring a resistance to shocks). It is possible that their raw materials partly conditioned their final shape. PSBs can comprise a wide variety of artefacts, that for some could have change of status (e.g., from cores to percussive tools), diffused, adapted but also reinvented over two million years.

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Exploring the Geometric Space of Metal-Organic Polyhedrons (MOPs) of Metal-Oxo Clusters.

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