Crystal supramolecularity: extended aryl embraces in dimorphs of [Cu(1,10-phen)2I]I3

Horn, Caitlin; Ali, Basem F.; Dance, Ian G.; Scudder, Marcia L.; Craig, Don

doi:10.1039/a910231k

Cited by 25 publications

(25 citation statements)

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“…The generated stacking patterns, identical for both phen ligands due to the C 2 symmetry of the molecular complex, result in rod-like aggregates along the [101] direction(Figure 2a). The separations between the centroids of the overlapping rings of 3.538 Å(Figure 2b) and the interplanar separation of 3.498 Å indicate the face-to-face stacking.43−45 The metal···metal separation through the stacked ligands is 8.070(3) Å.Figure 2cdemonstrates the mode of enclathration of methanol molecules in the crystal lattice.Inspection of the reported data for the landscape of mononuclear complexes {[Cu(phen) 2 (SO 4 )] solv} (solv = methanol, ethanol, ethane-1,2-diol, propane-1,3-diol, propane-1,2-diol, butane-2,3-diol), 34−38 where complex 1 represents the first missing member, reveals their isomorphic character indicated by preservation of the crystal symmetry (monoclinic, C) with the proportional increase of the unit cell dimensions, in favor of the robustness of the phen embracing46,47 in the absence of other stronger interactions and the possibility of accommodation of alcohol molecules close in structure and size in the alike crystal lattices.…”

mentioning

confidence: 99%

Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)₂] Sulfates

Melnic¹,

Coropceanu²,

Куликова³

et al. 2014

J. Phys. Chem. C

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Three mixed-ligand Cu(II) complexes with compositions [Cu(phen) 2 (SO 4 )]·CH 3 OH (1), [Cu(phen) 2 (SO 4 )]-(H 2 O) 2 (dmf) (2), and [Cu(phen) 2 H 2 O](SO 4 )(H 2 O) 4 (3), where phen = 1,10-phenanthroline and dmf = N,N′-dimethylformamide, were prepared and studied. These compounds belong to the landscape of the mononuclear Cu(phen) 2 sulfates, and the solvated complexes undergo frequent anion/water exchange at the metal center in aqueous solutions. Complexes are similar by the metal trigonal bipyramidal coordination geometry but differ by the mode of enclathration and number of protic and aprotic solvent guest molecules being accommodated in the crystal lattice. Crystal packing in 1−3 is determined by the robust supramolecular patterns that consist of stacking interactions between the planar extended phen fragments. These are observed in all three solids regardless of the interplay of other noncovalent interactions, including rather strong hydrogen bonds. The dual luminescence is detected at 580 and 470 nm for both crystals of phen and 3. Detailed analysis of singlet and triplet excitations in phen and 3 is performed by time-dependent density functional methods. Fluorescence is predicted with a low quantum yield at 386 nm, and dual phosphorescence from n−π* and π−π* triplet states is predicted at 523 and 496 nm. Emission quenching was demonstrated for 3 and explained by nonradiative decay involving supramolecular stacking and low-lying metal-centered states. ■ INTRODUCTIONFor decades Cu(II) coordination compounds have been attractive targets for magneto-and biochemistry. 1,2 Engineering of metal−organic materials with specific properties using a molecular building blocks approach is possible only by understanding the interplay of different interactions involved in self-assembly processes. From a crystal engineering perspective, one of the advantages of using transition metal ions is that the shape of the main building block can be controlled by way of organic ligand-bound metal-containing modules in directions dictated by the coordination geometry of the metal center and by careful choice of the ligands. 3−8 Design strategies employing simultaneously coordination bonds, hydrogen bonds, and π−π stacking interactions in crystal engineering are mostly not well documented so far. 9 We are involved in engineering, structural studies, and evaluation of properties of low-dimensional clusters and coordination polymers that include the Cu(II)−phen building block and reveal the contribution of stacking interactions in the crystal packing. 10,11 The necessity of careful examination and disclosure of the robust recurring patterns in such lowdimensional solids is dictated by their wide exploitation as medicinal forms with obvious antitumor efficacy. It has been reported that, in particular, phen derivatives [Cu-(CH 3 COO) 2 (phen)] and [Cu(sal)(phen)] demonstrate approximately seven times higher activity than cisplatin against HepG2, A-498, and A-549 cancer cells. Among the factors that influence the cytotoxic activity, the...

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mentioning

confidence: 99%

Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)₂] Sulfates

Melnic¹,

Coropceanu²,

Куликова³

et al. 2014

J. Phys. Chem. C

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“…The extent of the distortion, could be a consequence of the sterically hindered biq ligand coordinating to copper(I) in the central core, although crystal packing forces could cause such distortion. The Cu-N bond distances are 1.9973 and 2.0185 Å (table 4) comparable to Cu-N bond distances in similar systems containing N-heterocyclic ligands [3,9,21,22].…”

Section: H-and 13 C-nmr Spectramentioning

confidence: 68%

“…Other metal complexes containing biq have been reported recently, cis-[Rh(biq) 2 [4,5]. Furthermore, supramolecular motifs were recognized in the crystal structures of metal complexes containing aryl groups such as 2,2 0 -bipyridine [6], terpyridine ligands [7], and 1,10-phenanthroline [8,9]. Unusual oxidation states could also be trapped and isolated using this strategy of forming stable lattices [10].…”

Section: Introductionmentioning

confidence: 93%

“…(i) The strong bands appearing in the range 1420-1599 and 735-840 cm À1 in the IR spectra of the complexes, assigned to [(C¼C), (C¼N)] and (C-H), respectively, (2) 63(1) C (6) 5027 (2) À690 (2) 1222 (2) 53(1) C (7) 4306 (2) À162 (2) 1700 (2) 57(1) C (8) 4527 (2) 735 (2) 2354 (2) 53(1) C (9) 5496 (1) 1139 (2) 2550 (2) 44(1) C (10) 5800 (1) 2121 (2) 3259 (2) 46(1) C (11) 5153 (2) 2702 (2) 3813 (2) 57(1) C(12) 5496 (2) 3563 (2) 4465 (2) 60(1) C (13) 6480 (2) 3911 (2) 4563 (2) 54(1) C (14) 6897 (2) 4795 (2) 5230 (2) 65(1) C (15) 7854 (2) 5093 (2) 5270 (2) 69(1) C (16) 8427 (2) 4523 (3) 4671 (2) 71(1) C (17) 8064 (2) 3642 (2) 4033 (2) 61(1) C …”

Section: Ir Spectraunclassified

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Interconversion of copper(II) to copper(I): synthesis, characterization of copper(II) and copper(I) 2,2′-biquinoline complexes and their microbiological activity

Ali

Al-Sou’od

Al-Ja'ar

et al. 2005

Journal of Coordination Chemistry

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“…The distances were all comparable to those obtained in our study which considered C···C distances (in the range 3.443-3.780 Å) and cetroide···centroide distances (3.779 Å). Similar supramolecular motifs were recognized in the crystal structures of metal complexes containing aryl groups such as 2,2 -bypyridine [25], 1,10-phenanthroline [26], and 2,2 : 6 ,2 -terpyridyl complexes [27]. Nonclassical C-H···S intermolecular interactions have been recognised previously in some crystal structures containing sulfur atoms in organic molecules [28,29] as well as inorganic complexes [30][31][32].…”

Section: Intermolecular Interactionsmentioning

confidence: 96%

(π)C—H···S, (allyl)C—H···C(π) and π···π intermolecular interactions: synthesis, characterization, and crystal structure of 2,2′-bipyridine bis(diallyldithiocarbamato)zinc(II)

et al. 2006

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A mixed-ligand Zn(II) complex formulated as [Zn(aldtc) 2 (bipy)] (aldtc = diallyldithiocarbamate; bipy = 2,2 -bipyridine) was synthesized and characterized by IR, 1 H and 13 C NMR spectral measurements and Xray crystallography. The crystal structure of this complex indicates that Zn has a distorted octahedral geometry. The Zn-N distances are invariant (2.168(2) Å), while those of the Zn-S are slightly different (2.5408(9) and 2.5440(9) Å). The N-Zn-N, S-Zn-S and N-Zn-S bond angles are in the range 75.35(13)-99.75(7) • , 70.48(3)-161.02(5) • and 95.26(7)-160.32(7) • , respectively. The crystal packing of the complex shows different motifs of supramolecularity resulting from both hydrophilic ((π )C-H···S) and hydrophobic ((allyl)C-H···C(π )) intermolecular interactions. These interactions result in a chain arrangement of molecules along crystallographic c axis and the chains are further connected via π ···π stacking along with ((π )C-H···S along b axis leading to an overall crystal packing that can be regarded as layers of complexes along bc plane, which are held

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Crystal supramolecularity: extended aryl embraces in dimorphs of [Cu(1,10-phen)2I]I3

Cited by 25 publications

References 0 publications

Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)₂] Sulfates

Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)₂] Sulfates

Interconversion of copper(II) to copper(I): synthesis, characterization of copper(II) and copper(I) 2,2′-biquinoline complexes and their microbiological activity

(π)C—H···S, (allyl)C—H···C(π) and π···π intermolecular interactions: synthesis, characterization, and crystal structure of 2,2′-bipyridine bis(diallyldithiocarbamato)zinc(II)

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Crystal supramolecularity: extended aryl embraces in dimorphs of [Cu(1,10-phen)2I]I3

Cited by 25 publications

References 0 publications

Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)2] Sulfates

Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)2] Sulfates

Interconversion of copper(II) to copper(I): synthesis, characterization of copper(II) and copper(I) 2,2′-biquinoline complexes and their microbiological activity

(π)C—H···S, (allyl)C—H···C(π) and π···π intermolecular interactions: synthesis, characterization, and crystal structure of 2,2′-bipyridine bis(diallyldithiocarbamato)zinc(II)

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Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)₂] Sulfates

Robust Packing Patterns and Luminescence Quenching in Mononuclear [Cu(II)(phen)₂] Sulfates