Anion-dependent host–guest properties of porous assemblies of coordination complexes (PACs), [Cu(A)2(py)4] (A = PF6, BF4, CF3SO3, and CH3SO3; py = pyridine), based on Werner-type copper(ii) complexes in the solid state

Abstract

We report the syntheses and crystal structures of novel porous assemblies of coordination complexes (PACs) with/without guest molecules, α-[Cu(A)₂(py)₄] (α-PAC-2-A (A = PF₆, BF₄, CF₃SO₃, and CH₃SO₃); py = pyridine), γ-{[Cu(PF₆)₂(py)₄]·2guest} (γ-PAC-2-PF₆ ⊃ 2guest (guest = acetone and py)), γ-{[Cu(BF₄)₂(py)₄]·2acetone} (γ-PAC-2-BF₄ ⊃ 2acetone), and β-{[Cu(CH₃SO₃)₂(py)₄]·2.67H₂O} (β-PAC-2-CH₃SO₃ ⊃ 2.67H₂O). The single-crystal X-ray diffraction analyses of α-PAC-2-A show that α-PAC-2-A have dense packing structures, in which anions of the discrete coordination complexes form weak hydrogen-bonding and anion-π interactions. In contrast, γ-PAC-2-PF₆ ⊃ 2guest, γ-PAC-2-BF₄ ⊃ 2acetone, and β-PAC-2-CH₃SO₃ ⊃ 2.67H₂O form guest-including structures with coordination environments around the Cu(II) atoms similar to the α-forms. The vapour adsorption measurements for MeCN and acetone in α-PAC-2-A suggest that the adsorption associated with structural transformations is induced by weak Lewis-base PF₆⁻ and BF₄⁻ anions covered only with fluorine atoms, which weaken the host-host interactions.

High CO2/CH4 Selectivity of a Flexible Copper(II) Porous Coordination Polymer under Humid Conditions

“…In other words, the structural change from 1 ⊃2 acetone to 1 is irreversible and that from 1 to 1′ ⊃2 acetone is reversible. Similar behaviour has been observed in the related Cu II complex, [Cu(PF 6 ) 2 (pyridine) 4 ], which reversibly adsorbs acetone without the breaking of Cu−F bonds.…”

Emergence of chirality and structural complexity in single crystals at the molecular and morphological levels

“…The Cu 2+ centers are coordinately saturated and have four pyridine moieties of four TPEPA ligands positioned in the equatorial positions and two water molecules bound with their oxygen atoms in the axial positions. The origin of the chirality is induced by the arrangement of the four pyridine moieties around the metal center that generates a propeller-type conformation 35 . Each unit cells contains propellers having all the same handiness.…”

Chiral biomolecule based dodecanuclear dysprosium(iii)–copper(ii) clusters: structural analyses and magnetic properties

“…[1][2][3][4][5][6] Among these, coordination architectures pertaining to excellent symmetric features have been the most flanked ones owing to their captivating coordination environments, giving rise to utilitarian attributes as a consequence of their symmetry-aided structure-property correlation. [7][8][9][10][11][12][13] The inherent symmetry in such complexes makes the structure-property correlation much easier to priorly conceive, leading to a strategic rationale based design principle for attainment of targeted properties and therefore to gain an insight into the same.…”