Simple design for metal-based halogen-bonded cocrystals utilizing the M–Cl⋯I motif

Lisac, Katarina; Cinčić, Dominik

doi:10.1039/c8ce00754c

Cited by 30 publications

(18 citation statements)

References 72 publications

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“…From the beginning of the intensive research into halogen bonding at the turn of the millennium [1][2][3][4][5], one of the main areas of interest (apart from the fundamental studies of the nature and properties of the halogen bond) has been to utilize the halogen bond as a reliable non-covalent molecular interaction in supramolecular chemistry in general [6][7][8][9], and particularly in crystal engineering [10][11][12][13][14], as a means of the deliberate design of multi-component organic [15,16] and metal-organic [17][18][19][20] materials, both comprising ionic species (salts) [21][22][23][24][25][26] and neutral molecules (cocrystals) [27][28][29][30][31][32][33][34][35][36].…”

Section: Introductionmentioning

confidence: 99%

The Amine Group as Halogen Bond Acceptor in Cocrystals of Aromatic Diamines and Perfluorinated Iodobenzenes

et al. 2021

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In order to study the proclivity of primary amine groups to act as halogen bond acceptors, three aromatic diamines (p-phenylenediamine (pphda), benzidine (bnzd) and o-tolidine (otol)) were cocrystallised with three perfluorinated iodobenzenes (1,4-tetrafluorodiiodobenzene (14tfib), 1,3-tetrafluorodiiodobenzene (13tfib) and 1,3,5-trifluorotriiodobenzene (135tfib)) as halogen bond donors. Five cocrystals were obtained: (pphda)(14tfib), (bnzd)(13tfib)2, (bnzd)(135tfib)4, (otol)(14tfib) and (otol)(135tfib)2. In spite of the variability of both stoichiometries and structures of the cocrystals, in all the prepared cocrystals the amine groups form exclusively I···N halogen bonds, while the amine hydrogen atoms participate mostly in N–H⋯F contacts. The preference of the amine nitrogen atom toward the halogen bond, as opposed to the hydrogen bond (with amine as a donor), is rationalised by means of computed hydrogen and halogen bond energies, indicating that the halogen bond energy between a simple primary amine (methylamine) and a perfluorinated iodobenzene (pentafluoroiodobenze ne) is ca. 15 kJ mol−1 higher than the energy of the (H)NH∙∙∙NH2 hydrogen bond between two amine molecules.

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Section: Introductionmentioning

confidence: 99%

The Amine Group as Halogen Bond Acceptor in Cocrystals of Aromatic Diamines and Perfluorinated Iodobenzenes

et al. 2021

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“…[9][10][11][12][13] In contrast, the use of halogen bonding in coordination complexes, which are among the most diverse structures found in chemistry, remains comparatively unexplored. 14 In the studies that have been reported, three general strategies have emerged: firstly the design of ligands with an acceptor and donor in the same ligand (type i), [15][16][17] secondly cocrystals with either a neutral or cationic complex and halogen bonding donors (type ii) [18][19][20][21][22][23][24] and lastly complexes with two different ligands with one acting as the acceptor and the other the donor (type iii). The latter class typically uses halopyridine ligands and chelates such as -diketonates to balance the charge of the metal and satisfy the need for octahedral geometry.…”

Section: Introductionmentioning

confidence: 99%

Interplay of Halogen and Hydrogen Bonding in a Series of Heteroleptic iron(III) Complexes

Díaz-Torres¹,

Echeverría²,

Loveday³

et al. 2021

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<div>The influence of the halogen substituent on crystal packing and redox properties is investigated in a series of heteroleptic complexes [Fe(qsal-X)(dipic)]MeOH (qsal-X = 4-halogen-2-[(8-quinolylimino)methyl]phenolate; dipic = 2,6-pyridinedicarboxylate; X = F 1, Cl 2, Br 3 and I 4).</div><div>Compounds 1 and 2 exhibit triclinic symmetry (P1̅), whereas 3 and 4 crystallise in monoclinic P21/n. The crystal packing shows self-sorting of the ligands with - interactions between the qsal-X ligands and overlap of the dipic ligands to form a 1D chain, that is supported by C-H···O interactions. In 1 and 2, the cross-section of the 1D chain is square, while for 3 and 4, it is rectangular. In the former, the dipic ligands interact through C=O··· interactions, while - interactions are found in 3 and 4. Neighbouring chains are connected via - interactions involving the quinoline rings, but their relative position is driven by the preference of 1 and 2, for C-H···X interactions, whereas 3 and 4 form O···X halogen bonds. The nature and topology of the electron density of these interactions have been investigated using molecular electrostatic potential (MEP) mapping, quantum theory of atoms in molecules (QTAIM) and ‘non-covalent interactions’ (NCI) analysis. UV-Visible experiments show MLCT bands associated with the qsal-X ligands, confirming the structure is stable in solution. Electrochemical studies reveal slight tuning of the Fe3+/Fe2+ redox couple showing a linear relationship between E° and the Hammett parameter σp.</div><div><br></div>

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“…While there have been substantial studies into halogen bonding in single component metal-organic solids [30][31][32][33][34][35][36][37][38][39][40][41], synthesis of multi-component materials based on halogen-bonded metal-organic components has been receiving much less attention. Particularly scarce are studies involving cocrystals of neutral metal-organic components acting as halogen bond acceptors [42][43][44][45][46][47]. The most promising building blocks to date have been metal coordination complexes comprised of pendant acceptor groups such as halogenide ligands [46,47], chelating ligands such as imines [43], β-dicarbonyl compounds [14] and ligands with additional (non-coordinating) electron rich atoms or groups such as morpholine or thiomorpholine [48,49], which can form cocrystals with halogen bond donors, such as perfluorinated iodobenzenes.…”

Section: Introductionmentioning

confidence: 99%

“…Particularly scarce are studies involving cocrystals of neutral metal-organic components acting as halogen bond acceptors [42][43][44][45][46][47]. The most promising building blocks to date have been metal coordination complexes comprised of pendant acceptor groups such as halogenide ligands [46,47], chelating ligands such as imines [43], β-dicarbonyl compounds [14] and ligands with additional (non-coordinating) electron rich atoms or groups such as morpholine or thiomorpholine [48,49], which can form cocrystals with halogen bond donors, such as perfluorinated iodobenzenes.…”

Section: Introductionmentioning

confidence: 99%

Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals

et al. 2020

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In this work, we explore the halogen-bonded cocrystallization potential of cobaloxime complexes in the synthesis of cocrystals with perhalogenated benzenes. We demonstrate a strategy for synthesizing halogen-bonded metal–organic cocrystals by utilizing cobaloximes whose pendant bromide group and oxime oxygen enable halogen bonding. By combining three well-known halogen bond donor molecules differing in binding geometry and composition with three cobaloxime units, we obtained a total of four previously unreported cocrystals. Single crystal X-ray diffraction experiments showed that the majority of obtained cocrystals exhibited the formation of the targeted I···O and I···Br motives. These results illustrate the potential of cobaloximes as halogen bond acceptors and indicate that this type of halogen bond acceptors may offer a novel route to metal–organic halogen-bonded cocrystals.

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Simple design for metal-based halogen-bonded cocrystals utilizing the M–Cl⋯I motif

Abstract: The halogen bonding proclivity of the chlorine atom coordinated to the Co(ii) metal centre has been explored by synthesis and crystal structure analysis of a family of 12 novel metal-based halogen-bonded cocrystals with iodine-based donors.

Cited by 30 publications

References 72 publications

The Amine Group as Halogen Bond Acceptor in Cocrystals of Aromatic Diamines and Perfluorinated Iodobenzenes

The Amine Group as Halogen Bond Acceptor in Cocrystals of Aromatic Diamines and Perfluorinated Iodobenzenes

Interplay of Halogen and Hydrogen Bonding in a Series of Heteroleptic iron(III) Complexes

Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals

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