Amide-driven secondary building unit structural transformations between Zn(II) coordination polymers

Altres ajuts: J.P. acknowledges financial support from the CB615921 project, the CB616406 project from "Fundació La Caixa". D.E. acknowledges the PIF predoctoral fellowship from the Universitat Autònoma de Barcelona.The behavior of coordination polymers (CPs) against external stimuli has witnessed remarkable attention, especially when the resulting CPs present reversible molecular arrays. Accordingly, CPs with these characteristics can lead to differences in their properties owing to these structural differences, being promising for their use as potential molecular switches with diverse applications. Herein, we have synthesized four Zn(II) CPs bearing α-acetamidocinnamic acid (HACA) and 4,4'-bipyridine (4,4'-bipy). The reaction between Zn(OAc)2·2H2O, HACA, and 4,4'-bipy yields {[Zn(ACA)2(4,4'-bipy)]·EtOH}n (1), which was used for the formation of three CPs through dissolution-recrystallization structural transformations (DRSTs): {[Zn(ACA)2(4,4'-bipy)]·2MeOH}n (2), {[Zn2(μ-ACA)2(ACA)2(4,4'-bipy)]·2H2O}n (3), and {[Zn3(μ-ACA)6(4,4'-bipy)]·0.75CHCl3}n (4). The study of the four crystal structures revealed that their secondary building units (SBUs) comprise monomeric, dimeric, and trimeric arrangements linked by 4,4'-bipy ligands. The fundamental role of the utilized solvent and/or temperature, as well as their effect on the orientation of the amide moieties driving the formation of the different SBUs is discussed. Furthermore, the reversibility and interconversion between the four CPs have been assayed. Finally, their solid-state photoluminescence has evinced that the effect of the amide moieties not only predetermine a different SBU but also lead to a different emission in 4 compared with 1-3

Virtual assessment achieved two binary cocrystals based on a liquid and a solid pyridine derivative with modulated thermal stabilities

Altres ajuts: acords transformatius de la UABThe rational design of cocrystals triggered by the control of recurrent H-bonded patterns referred to as supramolecular synthons enabled the correlation between their structure and properties, which has been a topic of interest owing to the possibility to modulate them depending on the selected components. Accordingly, melting point has been one of the most studied properties, providing materials with enhanced thermal stability for specific applications. Within this frame, in this work we have selected a liquid and a solid pyridine derivative (dPy), namely 4-acetylpyridine (4-Acpy) and 2-hydroxypyridine (2-OHpy) to combine with carboxylic acids to obtain a pair of cocrystals. An initial virtual screening of some carboxylic acids based on the positive and negative critical points of the molecular electrostatic potential (MEP) surfaces was performed to evaluate the feasibility of cocrystal formation. This enabled us to select 1,3-benzodioxole-5-carboxylic acid (piperonylic acid, HPip) to combine with 4-Acpy andα-acetamidocinnamic acid (HACA) with 2-OHpy. Then, we have obtained the corresponding cocrystal experimentally by means of liquid-assisted grinding (LAG), and their crystal structures were elucidated, revealing the formation of (HPip)(4-Acpy) (1) and (HACA)(Pdon) (2) (Pdon = 2-pyridone), observing the tautomerization of 2-OHpy to Pdon. Both cocrystals were characterized by analytical and spectroscopic techniques. In addition, a Cambridge Structural Database (CSD) survey of 4-Acpy and Pdon in cocrystal systems was performed and the observed preferences regarding their preferable synthons and dimensionalities were shown. Finally, their melting points have been determined, and the resulting values have been correlated with the crystal packing of the compounds, supported by Hirshfeld surface analysis and energy framework

Ruthenium complexes of P-stereogenic phosphines with a heterocyclic substituent

The synthesis via phosphine-boranes of 13 new optically pure P-stereogenic diarylphosphines P(Het)PhR (Het = 4-dibenzofuranyl (DBF), 4-dibenzothiophenyl (DBT), 4-dibenzothiophenyl-S,S-dioxide (DBTO2) and 1-thianthrenyl (TA); R = OMe, Me, i-Pr, Fc (ferrocenyl)) following the Jugé-Stephan method is described. The ligands were designed with the aim of having a heteroatom in a position capable of interacting with a metal upon coordination. The ligands and their precursors have been fully characterised, including the determination of two crystal structures of phosphine-boranes. Ru neutral complexes of the type [RuCl2(η6-arene)(κP-P)] (arene = p-cymene and methyl benzoate) have been prepared and characterised, including three crystal structure determinations. Treatment of solutions of the complexes with TlPF6 allowed the preparation of well-defined cationic complexes [RuCl(η6-arene)(κ2P,S-P)]PF6 for DBT- and TA-based phosphines. The complexes possess a stereogenic Ru atom and in most of the cases they are present as a single isomer in solution. All the Ru complexes have been used in the asymmetric transfer hydrogenation of acetophenone in refluxing 2-propanol, with good activities and up to 70% ee

Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers

Altres ajuts: acord transformatiu CRUE-CSICAltres ajuts: Fundació La Caixa (projectes CB615921 i CB616406)The understanding of the effect generated by small differences of the organic ligands on the molecular and supramolecular arrangement of coordination polymers (CPs) is a key factor to control their properties. Therefore, the study of structurally related ligands differing in some factors inter alia functional group orientation, length, or functionality is a crucial task for crystal engineers. In this contribution, the reactions between Cd(OAc)2·2H2O, α-acetamidocinnamic acid (HACA) and different N,N-donor spacers with increasing length (pyrazine, pyz; 4,4'-bipyridine, 4,4'-bipy; 1,2-bis(4-pyridyl)ethylene, 1,2-bpe), as well as additional functionalities (4,4'-azopyridine, 4,4'-azpy) have been successfully performed. Their crystal structures have been elucidated revealing a family of ladder-type 1D CPs showing molecular arrays with single pillars for {[Cd2(μ-ACA)2(ACA)2(pyz)(H2O)2]·2EtOH}n (1), and double pillars for [Cd2(μ-ACA)2(ACA)2(4,4'-bipy)2]n (2), [Cd2(μ-ACA)2(ACA)2(1,2-bpe)2]n (3) and {[Cd2(μ-ACA)2(ACA)2(4,4'-azpy)2]·4,4'-azpy·9H2O}n (4). Remarkably, the effect of the addition of the azo group in 4 compared with 2 and 3 has led to a CP with the same molecular arrangement but different crystal packing, allowing the introduction of one non-coordinated 4,4'-azpy and nine water molecules. Finally, their solid-state UV-Vis and photoluminescence have been measured observing their blue-emitting properties

Construction of Zn(II) Linear Trinuclear Secondary Building Units from A Coordination Polymer Based on α-Acetamidocinnamic Acid and 4-Phenylpyridine

The synthesis and characterization of one coordination polymer and two trinuclear complexes are presented. The coordination polymer [Zn2(µ-O,O'-ACA)2(ACA)2(4-Phpy)2]n (1) has been obtained by the reaction between Zn(OAc)2·2H2O, α-acetamidocinnamic acid (HACA), and 4-phenylpyridine (4-Phpy) using EtOH as solvent. Its recrystallization in CH3CN or EtOH yields two trinuclear complexes, both having pinwheel arrays with formulas [Zn3(µ-ACA)6(4-Phpy)2]·4CH3CN (2·4CH3CN) and [Zn3(µ-ACA)6(EtOH)2]·4EtOH (3·4EtOH), respectively. These trinuclear species, unavoidably lose their solvent co-crystallized molecules at RT yielding the complexes [Zn3(µ-ACA)6(4-Phpy)2] (2) and [Zn3(µ-ACA)6(EtOH)2] (3). In addition, compound 2 has also been obtained reacting Zn(OAc)2·2H2O, HACA, and 4-Phpy in a 1:2:2 ratio using CH3CN as solvent. Compounds 1-3 have been characterized by analytical and spectroscopic techniques. Furthermore, single crystals suitable for X-ray diffraction method for compounds 1, 2·4CH3CN, and 3·4EtOH were obtained and their supramolecular interactions have been studied and discussed, showing 2D supramolecular planes for the trinuclear complexes and a 3D supramolecular network for the coordination polymer. Finally, the supramolecular interactions of 2·4CH3CN and 3·4EtOH have been compared using Hirshfeld surface analysis and electrostatic potential calculations

Neutral and Cationic Palladium Complexes of P-Stereogenic Phosphanes Bearing a Heterocyclic Substituent

The coordination chemistry of 13 optically pure P ‐stereogenic diarylmonophosphanes P(Het)PhR [Het = 4‐dibenzofuranyl (DBF), 4‐dibenzothiophenyl (DBT), 4‐dibenzothiophenyl S ,S ‐dioxide (DBTO2) and 1‐thianthrenyl (TA); R = OMe, Me, i Pr, Fc (ferrocenyl)] to Pd‐allyl moieties is described. Both neutral [PdCl(η3‐(2‐methylallyl)(κP ‐P )] and cationic [Pd{η3‐(2‐methylallyl)(κP ‐P )2}]PF6 complexes have been prepared. Coordination of the heteroatom of the heterocycle was only possible in the case of TA‐based phosphanes; these furnished complexes of the type [Pd{η3‐(2‐methylallyl)(κ2P,S ‐P )}]PF6 after chloride abstraction with TlPF6. The crystal structure of the complex [Pd(η3‐2‐methylallyl)(κ2P,S ‐PPh(OMe)(1‐TA)]PF6 is reported. The neutral Pd complexes were found to be highly active in the hydrovinylation of styrene after activation with AgBF4, except for the TA‐based phosphanes. The cationic Pd complexes were evaluated in allylic alkylation and amination with the model substrate rac ‐trans ‐1,3‐diphenylprop‐2‐enyl acetate (rac ‐I ), achieving total conversions and up to 70 % ee