Multiparameter High-Throughput and in Situ X-ray Diffraction Study of Six New Bismuth Sulfonatocarboxylates: Discovery, Phase Transformation, and Reaction Trends

Abstract

With the employment of high-throughput methods, the system Bi/4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (HDSNDC)/HO/additive (HNO or NaOH) was systematically investigated under hydrothermal reaction conditions. The influence of the molar ratio of the starting materials, pH, and reaction temperature and time was investigated in more than 500 reactions. The product formation is highly sensitive toward small changes of the synthesis parameters, but six new bismuth sulfonatocarboxylates were reproducibly obtained starting from clear solutions of the reactants. All compounds were structurally characterized from single-crystal X-ray diffraction data. Fully deprotonated linker ions are found in [BiO(OH)(HO)(DSNDC)] (1), [Bi(OH)(DSNDC)] (2), [BiO(OH)(HO)(DSNDC)] (3), and [BiO(OH)(HO)(DSNDC)]·4HO (4), while the presence of larger amounts of acid or short reaction times leads to compounds with noncoordinating -COOH groups, [Bi(OH)(HO)(DSNDC)(HDSNDC)] (5) and [BiO(OH)(HO)(HDSNDC)]· xHO (6), respectively. The inorganic building units (IBUs) in all six structures differ substantially from each other; the IBUs found in 2 ({Bi(OH)}), 5 (BiO polyhedron), and 6 ({BiO(OH)} cluster) have been reported in the literature, while new IBUs are observed for 1 (chains of composition {BiO(OH)}), 3 ({BiO(OH)} cluster), and 4 ({BiO(OH)} cluster). Systematic variation of the reaction temperature and time indicated their distinct influence on product formation. Hence, in situ powder X-ray diffraction measurements at Deutsches Elektronen-Synchrotron, Hamburg, Germany, employing synchrotron radiation were carried out. In all studied in situ reactions, compound 6 is first observed and subsequently transformed to 1, 2, 4, and 5, depending on the reaction time and temperature as well as concentration of the starting materials.

Homo‐ and Heteroleptic Coordination Polymers and Oxido Clusters of Bismuth(III) Vinylsulfonates

“…The cluster molecules do not interact with each other through coordinating bonds in the solid state (Figure ). This finding is in contrast to other bismuth oxido sulfonates such as the triflate, benzene‐1,2/1,3‐disulfonates, and 4,8‐disulfonyl‐2,6‐naphthalenedicarboxylates reported recently, which form polymeric networks in the solid state due to bridging sulfonato ligands.…”

“…The cluster moleculesd on ot interactw ithe ach other throughc oordinating bonds in the solid state ( Figure 6). This finding is in contrastt oo ther bismuth oxido sulfonates such as the triflate, [49] benzene-1,2/1,3-disulfonates, [73b] and 4,8-disulfonyl-2,6-naphthalenedicarboxylates [80] reported recently,w hich form polymeric networks in the solid state due to bridging sulfonato ligands. , which crystallizes in the triclinic space group P1 ,a re composed of one half of the centrosymmetric molecules 5 (see Figure S7 in the Supporting Information) and 6 (Figure 7a), respectively.…”

Building a Green, Robust, and Efficient Bi-MOF Heterogeneous Catalyst for the Strecker Reaction of Ketones

“…This building unit has already been observed in other materials combining bismuth and sulfonate-carboxylate linkers. 32 Joints of these SBUs through sulfonate or carboxylate oxygen atoms give rise to [Bi 14 O 27 ] layers, which are perpendicular to the [100] direction in a sql topological disposition. These oxo-hydroxo-bismutate inorganic layers are connected through the organic part to build a 3D framework ( Figure 3 ).…”

“…Thus, sulfonate-carboxylate linkers have already been successfully employed to synthesize a few bismuth MOFs with different types of inorganic SBUs, highlighting the structural richness that the use of this element offers for accessing new structures. 32 , 33 3,5-disulfobenzoic acid (H 3 DSB) is another tritopic organic linker combining carboxylic and sulfonic acid coordinating groups, which we have previously employed in the formation of several rare-earth MOFs, showing various types of polynuclear inorganic SBUs. 34 − 36 …”

Ψ-Polyhedral symbols for bismuth(III) with an active electron lone pair

“…In an CN = 8 environment, where the lone pair is active, one case of a cubic É-CU-8 geometry is found in an old report (Drew et al, 1990). The dodecahedral É-DD-8 system is found in several examples (Albat et al, 2017;Albat & Stock, 2018;Anamika et al, 2019;Feng et al, 2018a;Li et al, 2014;Morsali & Mahjoub, 2006;Pathak et al, 2015;Senior & Linden, 2020;Sharutin et al, 2004;Thurston et al, 2002;Wibowo et al, 2010Wibowo et al, , 2011bWibowo et al, , 2012; the number exceeds the smaller number of É-SAPR-8 examples (Albat & Stock, 2018;Koch & Ruck, 2010).…”