Supramolecular Isomerism in Coordination Compounds:  Nanoscale Molecular Hexagons and Chains

Abourahma, Heba; Moulton, Brian; Kravtsov, Victor Ch.; Zaworotko, Michael J.

doi:10.1021/ja027371v

Cited by 317 publications

(125 citation statements)

References 26 publications

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“…The sip ligands reported here coordinate to metal atoms in different coordination modes, namely as d-sip in MCCP-4 and e-sip in MCCP-5, respectively. With regards to the nip ligand, the only other metal-(nip) complexes which have been prepared are two Cu(nip) supramolecular isomers [11] and two Zn(nip) supramolecular structures, namely {[Zn(nip)(py)(…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal Syntheses, Crystal Structures and Photoluminescent Properties of Three Metal‐Cluster Based Coordination Polymers Containing Mixed Organic Ligands

et al. 2003

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Section: Introductionmentioning

confidence: 99%

Hydrothermal Syntheses, Crystal Structures and Photoluminescent Properties of Three Metal‐Cluster Based Coordination Polymers Containing Mixed Organic Ligands

et al. 2003

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“…We are aware of only one case in which a reaction has yielded both a discrete complex and an extended polymeric structure from the same building block. [7] However, we know of no examples in which these two general topologies were found to co-exist in a stable crystalline solid. Herein, we report the synthesis of a self-assembling, self-complementary metal complex that forms a supramolecular hexagon and a double-helical coordination polymer within a single crystalline lattice.…”

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confidence: 99%

Self‐Assembly of Two Distinct Supramolecular Motifs in a Single Crystalline Framework

2004

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Supramolecular chemistry is a rapidly growing field of research concerned with the construction of molecular assemblies held together by noncovalent interactions. [1,2] Forces such as hydrogen bonding, p-p stacking, and metalligand coordination have been extensively used in the synthesis of supramolecular structures. These assemblies are anticipated to find utility as new materials with novel catalytic, magnetic, electronic, and optical properties. [3][4][5][6] Within the realm of supramolecular complexes that utilize metal-ligand interactions, both discrete molecular species and coordination polymers have been investigated. We are aware of only one case in which a reaction has yielded both a discrete complex and an extended polymeric structure from the same building block.[7] However, we know of no examples in which these two general topologies were found to co-exist in a stable crystalline solid. Herein, we report the synthesis of a self-assembling, self-complementary metal complex that forms a supramolecular hexagon and a double-helical coordination polymer within a single crystalline lattice. Furthermore, it is proposed that aggregation of fluorine substituents is a key feature in directing the formation of this surprising example of supramolecular assembly.We have previously described heteroleptic copper(ii) complexes with dipyrromethene (dipyrrin) ligands [8] that can form self-complementary, one-dimensional "zig-zag" coordination polymers.[9] These complexes consist of square-planar copper(ii) centers bound by one dipyrrin ligand and one acetylacetonate (acac) ligand. The dipyrrin ligand features a second donor site (pyridyl nitrogen atom) that coordinates to the axial position of a neighboring copper(ii) center, thereby generating an extended structure. In an effort to explore the features of these complexes that would alter the polymeric structure, modifications of the acac ligand were pursued. Instead of using Cu(acac) 2 as the copper source, Cu(hfacac) 2 (hfacac = hexafluoroacetononate) was utilized, which resulted in a heteroleptic metal complex with a "blocking" hfacac ligand (Scheme 1). This change in the spectator ligand was found to noticeably alter the complexation behavior and supramolecular assembly of the heteroleptic compound.The products of the reaction between the dipyrrin ligand (4-pyrdpm = 5-(4-pyridyl)dipyrromethene, 2) and Cu(hfacac) 2 were found to be dependent on the component stoichiometry (Scheme 1). In situ generation of 2 combined with an excess of Cu(hfacac) 2 results in the isolation of the Scheme 1. Scheme for the synthesis of 4-pyrdpm (2) and heteroleptic copper complexes (3 and 4).

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“…3) and c g ···c g distance (Janiak, 2000) is 4.17 Å. The similar supramolecular synthons R 2 2 (10) and R 2 2 (12) (Bernstein et al, 1995) have been also observed in crystal structure of one dinuclear complex (Valigura et al, 2006) and several polymeric complexes (Abourahma et al, 2002;Burrows et al, 2008;Cao et al, 2008;Korabik et al, 2011;Maharramov et al, 2012;Vaskova et al, 2011;Xu et al, 2007;Yamada et al, 1998). The crystal packing of 1 is shown in Fig.…”

Section: Resultsmentioning

confidence: 70%

Structures of copper(II) 2-chlorobenzoate monohydrate and copper(II) 3,5-dichlorobenzoate trihydrate

Medvecká¹,

Halaška²,

Jomová³

et al. 2012

Acta Chimica Slovaca

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The crystal structures of the title compounds, [Cu 2 (µ2-2-Clbz) 4 cations are bridged through four 2-chlorobenzoate ligands. The Cu 2+ ion in 1 is pentacoordinated by four oxygen atoms of bridging 2-chlorobenzoate ligands and one coordinated water molecule. The compound 2 forms mononuclear complex, where the Cu 2+ ion is pentacoordinated by two oxygen atoms of monodentate 3,5-dichlorobenzoate ligands and three coordinated water molecule. Both complexes are connected through O-H···O hydrogen bonds into frameworks. The π-π stacking interactions are also observed in crystal structure of 2.

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Supramolecular Isomerism in Coordination Compounds: Nanoscale Molecular Hexagons and Chains

Abstract: A nanoscale supramolecular hexagon, 1, and its supramolecular isomeric chain structure, 2, have been prepared from self-assembly of 5-NO2-bdc and Cu(II) cations. The hexagon is neutral and soluble and has outer and inner diameters of 3.1 and 0.8 nm, respectively.

Cited by 317 publications

References 26 publications

Hydrothermal Syntheses, Crystal Structures and Photoluminescent Properties of Three Metal‐Cluster Based Coordination Polymers Containing Mixed Organic Ligands

Hydrothermal Syntheses, Crystal Structures and Photoluminescent Properties of Three Metal‐Cluster Based Coordination Polymers Containing Mixed Organic Ligands

Self‐Assembly of Two Distinct Supramolecular Motifs in a Single Crystalline Framework

Structures of copper(II) 2-chlorobenzoate monohydrate and copper(II) 3,5-dichlorobenzoate trihydrate

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