Synthesis, Structures and Co-Crystallizations of Perfluorophenyl Substituted β-Diketone and Triketone Compounds

Abstract

Perfluorophenyl-substituted compounds, 3-hydroxy-1,3-bis(pentafluorophenyl)-2- propen-1-one (H1) and 1,5-dihydroxy-1,5-bis(pentafluorophenyl)-1,4-pentadien-3-one (H22), were prepared in 56 and 30% yields, respectively, and only the enol forms were preferentially obtained among the keto-enol tautomerism. Molecular conformations and tautomerism of the fluorine-substituted compounds were certified based on X-ray crystallographic studies and density functional calculations. The solvent dependency of the absorption spectra was only observed for the fluorinated compounds. The compounds H1 and H22 quantitatively formed co-crystals with the corresponding non-perfluorinated compounds, dibenzoylmethane (H3) and 1,5-dihydroxy-1,5-diphenyl-1,4-pentadien-3-one (H24), respectively, through the arene–perfluoroarene interaction to give the 1:1 co-crystals H1•H3 and H22•H24, which were characterized by X-ray crystallographic and elemental analysis studies.

Enhanced and Heteromolecular Guest Encapsulation in Nonporous Crystals of a Perfluorinated Triketonato Dinuclear Copper Complex

“…Complex 2 was obtained as a dark green powder by the reaction of 1,5‐bis(pentafluorophenyl)‐1,3,5‐pentanetrione (H 2 L) with CuCl 2 ⋅ 2 H 2 O. Typically, a solution of H 2 L (223 mg, 0.5 mmol) and NaOCH 3 (54 mg, 1.0 mmol) in methanol (13 mL) was added dropwise to a solution of CuCl 2 ⋅ 2 H 2 O (855 mg, 0.5 mmol) in methanol (3 mL), and the mixture was stirred for 2 h. After removing the solvent, the residue was extracted with CHCl 3 , which was further evaporated to give a dark green powder (yield: 99 %).…”

“…Preparation of 2 : the complex was prepared from CuCl 2 ⋅ 2 H 2 O and 1,5‐bis(pentafluorophenyl)‐1,3,5‐pentanetrione, as previously reported . Typically, to a solution of the corresponding ligand (0.5 mmol) in MeOH (10 mL), were added a solution of NaOMe (1 mmol) in MeOH (3 mL) and a solution of CuCl 2 ⋅ 2 H 2 O (0.5 mmol) in MeOH (3 mL).…”

Effect of hydrogen bonds and π⋯π interactions on the crystallization of phenyl-perfluorophenyl amides: understanding the self-organization of a cocrystal

“…2,3 In particular, cocrystals containing phenyl-perfluorophenyl recognition have received special attention. In addition to investigating specific arenepolyfluoroarene compounds, [4][5][6] the phenyl-perfluorophenyl stacking has been used in the presence of functional groups such as disulfides, 7 imines, 8 olefinic compounds, [9][10][11] halogen substitutions, 12,13 ketones, 14 carboxylic acids, 15 carboxylic acids-amides, 16 and carboxylic acids-imines. 17 The crystal packing of the structures mentioned in the literature generally exhibit donor-acceptor interactions, where the authors highlight the aryl directionality or cooperation with other strong interactions between the mains dimers.…”

Selective recognition and reversible encapsulation of tetrameric alcohol clusters via hydrogen bonds using a perfluorinated dinuclear nickel(ii) complex

“…The crystal structures of the corresponding Cu 2+ complex 2, which were prepared using a previously reported protocol, 15,26 from EtOH and MeOH show coordinated alcohols but the number of molecules and the coordination geometries are different to those found using the same protocols for the crystallization of 1; i.e., brown crystals of 2•2EtOH and 2•2MeOH are obtained and Cu 2+ centers exhibit a five coordinated square pyramidal geometry with one alcohol coordination (Fig. 3c and d).…”

“…25 These backgrounds prompted us to investigate a Ni 2+ complex that (a) can switch its coordination geometry between hexa-coordinated octahedral and tetra-coordinated planar, (b) can form co-crystals with guest inserted cavities at the axial position of the Ni 2+ ions, and (c) exhibit reversible and enhanced insertion behavior of alcohol compounds. Thus, as a development of host crystals that include solvent molecules, we synthesized a dinuclear Ni 2+ complex ( 1 ) using the pentafluorophenyl-substituted triketonate ligand, H 2 L, 26 to help understand the intermolecular interactions between the complex and alcohol molecules (Scheme 1). Complex 1 gives unique crystals 1 ·2EtOH·2H 2 O and 1 ·8MeOH from solutions of EtOH and MeOH, respectively.…”