Fluorine‐Substituted Ligands Induce Structural Diversity of Coordination Compounds

Khavasi, Hamid Reza; Rahimi, Narjes

doi:10.1002/slct.201702047

Cited by 6 publications

(3 citation statements)

References 76 publications

(36 reference statements)

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“…Khavasi and Rahimi [125] have also demonstrated the importance of F···F interactions in crystals. They noted that in coordination compounds fluorinated ligands exercise influence not only on the first coordination sphere but also on the supramolecular architecture and overall construction of the compounds [126]. It was shown that the two-dimensional polymeric complexes of N-(fluorinatedphenyl)-2-pyrazinecarboxamides ligands, carrying three and four fluorine atoms on phenyl rings, were stabilized by F···F type-II synthons between adjacent rings, in addition to participating in F···π interactions.…”

Section: Evidence Of F···f Interactions In Molecules and Crystalsmentioning

confidence: 99%

“…Figure 12 shows an example of the unit-cell of a fluorine reinforced system required for the development of the 4,4 -bis(nonafluorobutyl)-2,2 -bipyridine crystal [131], wherein F···F intermolecular distances vary between 2.9 and 3.4 Å. Figure 13 first coordination sphere but also on the supramolecular architecture and overall construction of the compounds [126]. It was shown that the two-dimensional polymeric complexes of N-(fluorinatedphenyl)-2-pyrazinecarboxamides ligands, carrying three and four fluorine atoms on phenyl rings, were stabilized by F···F type-II synthons between adjacent rings, in addition to participating in F···π interactions.…”

Section: Evidence Of F···f Interactions In Molecules and Crystalsmentioning

confidence: 99%

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Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Varadwaj

Marques

et al. 2018

Computation

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The divergence of fluorine-based systems and significance of their nascent non-covalent chemistry in molecular assemblies are presented in a brief review of the field. Emphasis has been placed to show that type-I and -II halogen-centered F···F long-ranged intermolecular distances viable between the entirely negative fluorine atoms in some fluoro-substituted dimers of C 6 H 6 can be regarded as the consequence of significant non-covalent attractive interactions. Such attractive interactions observed in the solid-state structures of C 6 F 6 and other similar fluorine-substituted aromatic compounds have frequently been underappreciated. While these are often ascribed to crystal packing effects, we show using first-principles level calculations that these are much more fundamental in nature. The stability and reliability of these interactions are supported by their negative binding energies that emerge from a supermolecular procedure using MP2 (second-order Møller-Plesset perturbation theory), and from the Symmetry Adapted Perturbation Theory, in which the latter does not determine the interaction energy by computing the total energy of the monomers or dimer. Quantum Theory of Atoms in Molecules and Reduced Density Gradient Non-Covalent Index charge-density-based approaches confirm the F···F contacts are a consequence of attraction by their unified bond path (and bond critical point) and isosurface charge density topologies, respectively. These interactions can be explained neither by the so-called molecular electrostatic surface potential (MESP) model approach that often demonstrates attraction between sites of opposite electrostatic surface potential by means of Coulomb's law of electrostatics, nor purely by the effect of electrostatic polarization. We provide evidence against the standalone use of this approach and the overlooking of other approaches, as the former does not allow for the calculation of the electrostatic potential on the surfaces of the overlapping atoms on the monomers as in the equilibrium geometry of a complex. This study thus provides unequivocal evidence of the limitation of the MESP approach for its use in gaining insight into the nature of reactivity of overlapped interacting atoms and the intermolecular interactions involved.

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Section: Evidence Of F···f Interactions In Molecules and Crystalsmentioning

confidence: 99%

Section: Evidence Of F···f Interactions In Molecules and Crystalsmentioning

confidence: 99%

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Varadwaj

Marques

et al. 2018

Computation

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“…A careful examination of the reported crystal networks shows that there are Cl···Hg, Br···Hg, and O···Hg interactions that can be responsible for bringing together the aromatic rings (Figure ). Khavasi reported these long coordination bonds for similar compounds, − and Puddephatt and his group reported a series of Hg(II) coordination compounds which reveal that long coordination bonds direct the assembly of coordination polymers . Therefore, the closeness of aromatic rings in the crystal networks is not necessarily due to an attractive interaction between them.…”

Section: Introductionmentioning

confidence: 99%

Controlling π–π Interactions through Coordination Bond Formation: Assembly of 1-D Chains of acac-Based Coordination Compounds

León-Zárate

Valdés-Martı́nez

2021

Crystal Growth & Design

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We present a new approach for the construction of 1-D chains of acac-based copper coordination compounds assembled through π−π aromatic interactions. We use 3-(phenylethynyl)pyridine derivatives as ligands that can establish aromatic interactions to intermolecularly bind the coordination compounds. The crystal networks of the free pyridines show that there is no control over aromatic interactions, since different interactions are present. On the other hand, the supramolecular behavior of the coordination compounds is very homogeneous since, in all of the crystal networks, the intended 1-D chains are present. Given the polarization of the aromatic rings due to coordination, reflected in the calculated molecular electrostatic potential maps, we gain control over the π−π interaction geometry, promoting a head to tail interaction between the coordinated 3-(phenylethynyl)pyridines. This strategy to constructing 1-D chains is reliable and reproducible; thus, these types of π−π aromatic interactions are a useful supramolecular tool to control the molecular assembly in the solid state.

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Phenomenal Observation of Attractive Intermolecular CH⋯HC Interaction in a Mercury (II) Complex: An Experimental and First‐Principles Study

Khavasi

Balmohammadi

2019

ChemistrySelect

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The nature of the attractive intermolecular CÀ H…HÀ C interaction, which could affect the crystal packing and solid-state molecular structure, is yet unknown. Here, a novel mercury (II) complex including N-(2-biphenyl)pyrazine-2-carboxamide ligand, one such system, has been synthesized and characterized by a single crystal X-ray diffraction. The existence of attractive intermolecular CÀ H⋯HÀ C interaction (-2.64 to À 9.30 kj/mol depending on computational levels) is a notable feature in the crystal packing of this complex, which is the first observation of intermolecular CÀ H⋯HÀ C interaction in a metal complex. From crystallographic data, this contact has a distance of 2.172 Å which is 9.5% shorter than the sum of the van der Waals radii of two hydrogen atoms, which is the primary condition of having intermolecular interactions. We study the nature CÀ H… HÀ C interaction in the synthesized mercury (II) complex using periodic/non-periodic density functional theory in conjunction with quantum theory of atoms in molecules, non-covalent interaction reduced density gradient method, natural bond orbital, and energy decomposition analysis tools. Our results suggest that CÀ H⋯HÀ C interaction has closed-shell, donoracceptor, and van der Waals nature.[a] Prof.

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Fluorine‐Substituted Ligands Induce Structural Diversity of Coordination Compounds

Cited by 6 publications

References 76 publications

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Can Combined Electrostatic and Polarization Effects Alone Explain the F···F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective

Controlling π–π Interactions through Coordination Bond Formation: Assembly of 1-D Chains of acac-Based Coordination Compounds

Phenomenal Observation of Attractive Intermolecular CH⋯HC Interaction in a Mercury (II) Complex: An Experimental and First‐Principles Study

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