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

Habuka, Yusuke; Usui, Hirotomo; Okawa, Mizuki; Shinohara, Takanori; Yuge, Hidetaka; Mao, Yuchen; Gong, Jin; Richards, Gary J.; Hori, Akiko

doi:10.1039/d4ce00166d

CrystEngComm

2024

DOI: 10.1039/d4ce00166d

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

Yusuke Habuka,

Hirotomo Usui,

Mizuki Okawa

et al.

Abstract: A perfluorinated Ni(ii) complex encapsulates MeOH, forming unique tetrameric clusters stabilized by hydrogen bonding in the crystal to achieve remarkable uptake of MeOH over EtOH and water, demonstrating potential for separation and sensing.

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Co-Crystallization and Structural Studies of Benzophenone Recognized by Positively Shifted ESPs of Perfluorinated β-Diketonate Complexes (M = Cu, Pd, Pt)

Kobayashi,

Ikumura,

Lee

et al. 2024

Crystals

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Benzophenone was encapsulated in molecular crystals of fully fluorinated coordination complexes, [ML2] [1, M = Cu2+ and Pd2+, L = bis(pentafluorobenzoyl)-methanido−], forming a unique chiral co-crystal with a ratio of [ML2]:benzophenone = 2:3, while no encapsulation was observed in the corresponding non-fluorinated complexes [M(dbm)2] (dbm = dibenzoylmethanido−). Notable π-hole···π and metal(M)···π interactions were detected between the complex and the adapted orientation of benzophenone in the co-crystals. Analyses from crystal structures and thermogravimetric (TG) results indicated that the encapsulation and thermal stability of benzophenone in these molecular crystals correlate well with the electrophilic characteristics shown by the electrostatic potential (ESP) at the metal centers, which is enhanced by fluorination: Cu2+ > Pd2+ >> Pt2+. The recognition of benzophenone is driven by π-holes created by the electron-withdrawing nature of fluorine atoms and the electron-deficient metal ion enhanced by the aromatic fluorine, demonstrating that the effect of electrostatic molecular recognition is as significant as oxygen coordination, as shown in comparative studies with 1,1-diphenylethylene.

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Co-Crystallization and Structural Studies of Benzophenone Recognized by Positively Shifted ESPs of Perfluorinated β-Diketonate Complexes (M = Cu, Pd, Pt)

Kobayashi,

Ikumura,

Lee

et al. 2024

Crystals

View full text Add to dashboard Cite

show abstract

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

Abstract: A perfluorinated Ni(ii) complex encapsulates MeOH, forming unique tetrameric clusters stabilized by hydrogen bonding in the crystal to achieve remarkable uptake of MeOH over EtOH and water, demonstrating potential for separation and sensing.

Cited by 1 publication

References 46 publications

Co-Crystallization and Structural Studies of Benzophenone Recognized by Positively Shifted ESPs of Perfluorinated β-Diketonate Complexes (M = Cu, Pd, Pt)

Co-Crystallization and Structural Studies of Benzophenone Recognized by Positively Shifted ESPs of Perfluorinated β-Diketonate Complexes (M = Cu, Pd, Pt)

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