A counter ion triggers stabilization of two geometrical isomers of a Ni(<scp>ii</scp>) dication diradical porphyrin dimer: the role of anion–π interactions

Pandey, Anjani K.; Usman, Mohammad; Rath, Sankar Prasad

doi:10.1039/c9cc02902h

Cited by 11 publications

(2 citation statements)

References 36 publications

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“…There are only scant findings of closely related interactions within crystals that might serve as a basis of comparison. Among those pairing SbCl 3 with a N-base, 70,71 the most closely connected to the computations described above places the N of aniline 72 within 2.53 Å of Sb, fairly close to the 2.69 Å distance calculated here for the NH 3 base. Further, the θ(ClSb••N) angle in the X-ray structure is nearly precisely equal to the 165°o btained from the geometry optimization.…”

Section: 1supporting

confidence: 82%

Transition between the Noncovalency and Covalency of σ–Hole Bonds

Scheiner

2023

J. Phys. Chem. A

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The properties of the bond between a N-ligand and a Lewis acid containing a σ−hole are studied by quantum chemical methods. Interactions considered include pnicogen bonds involving SbX 5 , PX 5 , and PX 3 , where X represents any of the halogen atoms F, Cl, Br, or I. Also studied are the tetrel bonds of PbX 4 and SiX 4 , as well as the chalcogen bond involving TeOX 4 . Both NH 3 and NCH are applied as two possible bases of differing potency. Some of the bonds are very strong with interaction energies easily exceeding 25 kcal/mol and with AIM bond critical point densities much higher than 0.04 au, suggesting their classification as coordinate covalent bonds. The pentavalent SbX 5 and PX 5 fall into this category when combined with NH 3 , as does TeOX 4 . Although the tetrel bonds involving PbX 4 are only slightly weaker, they are probably better viewed as a strong noncovalent bond on the cusp of covalency. Changing the internal bonding of hypervalent SbX 5 to the more conventional SbX 3 weakens the interaction to a classical noncovalent pnicogen bond. Reducing the base nucleophilicity from NH 3 to NCH weakens the bonds so that they are clearly noncovalent.

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Section: 1supporting

confidence: 82%

Transition between the Noncovalency and Covalency of σ–Hole Bonds

Scheiner

2023

J. Phys. Chem. A

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“…[9] Anion-π interactions are shown to be of great importance in systems containing coordination and organometallic compounds. [32,33] Transition metal coordination is known to enhance the strength of various interactions, most notably hydrogen bonding [34] and stacking interactions. [35,36] Theoretical and experimental studies have also shown that pyridine can form anion-π interactions only if its nitrogen is coordinated with silver(I), [37] while silver(I) coordination of all nitrogen atoms of pyrazine and s-tetrazine dramatically strengthens their anionπ interactions.…”

Section: Introductionmentioning

confidence: 99%

New Type of Aromatic π‐Systems for Anion Recognition: Strong Anion‐π and C−H⋅⋅⋅Anion Interactions Between Halides and Aromatic Ligands in Half‐Sandwich Compounds

Malenov

Zarić

2021

Chemistry A European J

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Half-sandwich compounds of benzene, cyclopentadienyl, pentamethylcyclopentadienyl, and indenyl were studied as a new type of aromatic π-systems for interactions with halide anions. Although uncoordinated benzene forms only CÀ H•••anion interactions, and hexafluorobenzene forms only anion-π interactions, aromatic ligands in half-sandwich compounds can form both types of interactions, because their entire electrostatic potential surface is positive. These aromatic ligands can form stronger anion-π interactions than organic aromatic molecules, as a consequence of more pronounced dispersion and induction energy components. Moreover, CÀ H•••anion interactions of aromatic ligands are stronger than anion-π interactions, and significantly stronger than CÀ H•••anion interactions of benzene. Our study shows that transition-metal coordination can make aromatic moieties suitable for strong interactions with anions, and gives insight into the design of new anion receptors.

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Through‐Space Spin Coupling in a Silver(II) Porphyrin Dimer upon Stepwise Oxidations: Ag^II⋅⋅⋅Ag^II, Ag^II⋅⋅⋅Ag^III, and Ag^III⋅⋅⋅Ag^IIIMetallophilic Interactions

Singh¹,

Usman²,

Sciortino

et al. 2019

Chemistry A European J

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Metallophilic interactions between closed‐shell metal ions are becoming a popular tool for a variety of applications related to high‐end materials. Heavier d8 transition‐metal ions are also considered to have a closed shell and can be involved in such interactions. There is no systematic investigation so far to estimate the structure and energy characteristics of metallophilic interactions in AgII/AgII (d9/d9), AgIII/AgIII (d8/d8), and mixed‐valent AgII/AgIII (d9/d8) complexes, which have been demonstrated in the present study. Both interporphyrinic and intermetallic interactions were investigated on stepwise oxidation by using a rigid ethene‐bridged cis silver(II) porphyrin dimer and the results compared with those for highly flexible ethane‐bridged analogues. By controlling the nature of chemical oxidants and their stoichiometry, both 1e and 2e oxidations were done stepwise to generate AgII/AgIII mixed‐valent and AgIII/AgIII porphyrin dimers, respectively. Unlike all other ethene‐bridged metalloporphyrin dimers reported earlier, in which 2e oxidation stabilizes only the trans form, such an oxidation of silver(II) porphyrin dimer stabilizes only the cis form because of the metallophilic interaction. Besides silver(II)⋅⋅⋅silver(II) interactions in cis silver(II) porphyrin dimer, stepwise oxidations also enabled us to achieve various hitherto‐unknown silver(II)⋅⋅⋅silver(III) and silver(III)⋅⋅⋅silver(III) interactions, which thereby allow significant modulation of their structure and properties. The strength of Ag⋅⋅⋅Ag interaction follows the order AgII/AgII (d9/d9)

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A counter ion triggers stabilization of two geometrical isomers of a Ni(ii) dication diradical porphyrin dimer: the role of anion–π interactions

Abstract: Two isomers of a nickel(ii)porphyrinato dication diradical, isolated selectively in pure form, are stabilized exclusively by anion–π interactions, have unique and distinct electronic and spectroscopic features and display an anion-induced charge/electron transfer phenomenon.

Cited by 11 publications

References 36 publications

Transition between the Noncovalency and Covalency of σ–Hole Bonds

Transition between the Noncovalency and Covalency of σ–Hole Bonds

New Type of Aromatic π‐Systems for Anion Recognition: Strong Anion‐π and C−H⋅⋅⋅Anion Interactions Between Halides and Aromatic Ligands in Half‐Sandwich Compounds

Through‐Space Spin Coupling in a Silver(II) Porphyrin Dimer upon Stepwise Oxidations: Ag^II⋅⋅⋅Ag^II, Ag^II⋅⋅⋅Ag^III, and Ag^III⋅⋅⋅Ag^IIIMetallophilic Interactions

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A counter ion triggers stabilization of two geometrical isomers of a Ni(ii) dication diradical porphyrin dimer: the role of anion–π interactions

Abstract: Two isomers of a nickel(ii)porphyrinato dication diradical, isolated selectively in pure form, are stabilized exclusively by anion–π interactions, have unique and distinct electronic and spectroscopic features and display an anion-induced charge/electron transfer phenomenon.

Cited by 11 publications

References 36 publications

Transition between the Noncovalency and Covalency of σ–Hole Bonds

Transition between the Noncovalency and Covalency of σ–Hole Bonds

New Type of Aromatic π‐Systems for Anion Recognition: Strong Anion‐π and C−H⋅⋅⋅Anion Interactions Between Halides and Aromatic Ligands in Half‐Sandwich Compounds

Through‐Space Spin Coupling in a Silver(II) Porphyrin Dimer upon Stepwise Oxidations: AgII⋅⋅⋅AgII, AgII⋅⋅⋅AgIII, and AgIII⋅⋅⋅AgIIIMetallophilic Interactions

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Through‐Space Spin Coupling in a Silver(II) Porphyrin Dimer upon Stepwise Oxidations: Ag^II⋅⋅⋅Ag^II, Ag^II⋅⋅⋅Ag^III, and Ag^III⋅⋅⋅Ag^IIIMetallophilic Interactions