A Large Family of Halogen-Bonded Cocrystals Involving Metal–Organic Building Blocks with Open Coordination Sites

Nemec, Vinko; Fotović, Luka; Friščić, Tomislav; Cinčić, Dominik

doi:10.1021/acs.cgd.7b01325

Cited by 47 publications

(30 citation statements)

References 43 publications

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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

Preprint

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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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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

Preprint

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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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“…Halogen bond (XB) has found to be a useful tool in crystal engineering in recent years due to its strength and directional preferences [1][2][3][4][5][6]. A molecular entity with electrophilic region on a halogen atom is defined as XB donor, while an entity with nucleophilic region, i.e., Lewis base, is defined as an XB acceptor [7].…”

Section: Introductionmentioning

confidence: 99%

Extended Assemblies of Ru(bpy)(CO)2X2 (X = Cl, Br, I) Molecules Linked by 1,4-Diiodotetrafluoro-Benzene (DITFB) Halogen Bond Donors

2019

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The ruthenium carbonyl compounds, Ru(bpy)(CO)2X2 (X = Cl, Br or I) act as neutral halogen bond (XB) acceptors when co-crystallized with 1,4-diiodotetrafluoro-benzene (DITFB). The halogen bonding strength of the Ru-X⋅⋅⋅I halogen bonds follow the nucleophilic character of the halido ligand. The strongest halogen bond occurs between the chlorido ligand and the iodide atoms of the DITFB. All three halogen bonded complexes form polymeric assemblies in the solid state. In Ru(bpy)(CO)2Cl2⋅DITFB (1) and in Ru(bpy)(CO)2Br2⋅DITFB (2) both halido ligands are halogen bonded to only one DITFB donor. In Ru(bpy)(CO)2I2⋅DITFB (3) only one of the halido ligands is involved in halogen bonding acting as ditopic center for two DITFB donors. The polymeric structures of 1 and 2 are isomorphic wave-like single chain systems, while the iodine complexes form pairs of linear chains attached together with weak F⋅⋅⋅O≡C interactions between the closest neighbors. The stronger polarization of the iodide ligand compared to the Cl or Br ligands favors nearly linear C-I⋅⋅⋅I angles between the XB donor and the metal complex supporting the linear arrangement of the halogen bonded chain.

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A Large Family of Halogen-Bonded Cocrystals Involving Metal–Organic Building Blocks with Open Coordination Sites

Cited by 47 publications

References 43 publications

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

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

Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals

Extended Assemblies of Ru(bpy)(CO)2X2 (X = Cl, Br, I) Molecules Linked by 1,4-Diiodotetrafluoro-Benzene (DITFB) Halogen Bond Donors

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