scholarly journals Recurrent supramolecular motifs in discrete complexes and coordination polymers based on mercury halides: prevalence of chelate ring stacking and substituent effects

CrystEngComm ◽  
2018 ◽  
Vol 20 (8) ◽  
pp. 1065-1076 ◽  
Author(s):  
Ghodrat Mahmoudi ◽  
Jan K. Zaręba ◽  
Antonio Bauzá ◽  
Maciej Kubicki ◽  
Agata Bartyzel ◽  
...  
Keyword(s):  
Schiff Bases ◽  
Coordination Polymers ◽  
Chelate Ring ◽  
Substituent Effects ◽  
Dft Study ◽  
Stacking Interactions ◽  
X Ray ◽  
Supramolecular Motifs ◽  
Π Stacking ◽  
Mercury Halides

We report the synthesis, X-ray characterization and DFT study of five Hg(ii) complexes with Schiff bases containing a nicotinohydrazide core to explore the formation of chelate-ring π-stacking interactions.

scholarly journals Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)2] (Hhfacac = Hexafluoropentane-2,4-dione)

Inorganics ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 54
Author(s):  
Giacomo Manfroni ◽  
Simona S. Capomolla ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Coordination Polymers ◽  
Metal Binding ◽  
Polymer Chains ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
Preparative Scale ◽  
X Ray ◽  
Single Crystal Structures ◽  
Π Stacking ◽  
Packing Interactions

The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)2(2)]n.2nC6H5Me, [Cu2(hfacac)4(3)2]n.nC6H4Cl2, [Cu2(hfacac)4(3)2]n.nC6H5Cl, and [Cu(hfacac)2(4)]n.nC6H5Cl have been formed by reactions of 1, 2, 3 and 4 with [Cu(hfacac)2].H2O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 and [Cu(hfacac)2(2)]n.2nC6H5Me are zig-zag chains and the different substitution position of the CF3 group in 1 and 2 does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)2(4)]n.nC6H5Cl, the peripheral 3-CF3C6H4 unit is accommodated in a pocket between two {Cu(hfacac)2} units and engages in four C–Hphenyl...F–Chfacac contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating 1 and 2. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands 3 or 4.

Self-Recognizing π-π Stacking Interactions Designed for the Generation of Ultrastable Mesoporous Hydrogen-Bonded Organic Frameworks

2019 ◽  
Author(s):  
KAIKAI MA ◽  
Peng Li ◽  
John Xin ◽  
Yongwei Chen ◽  
Zhijie Chen ◽  
...  
Keyword(s):  
Pore Size ◽  
Fiber Composite ◽  
Aqueous Media ◽  
Stacking Interactions ◽  
Mustard Gas ◽  
X Ray Diffraction ◽  
X Ray ◽  
Expansion Strategy ◽  
Π Stacking ◽  
Hydrogen Bonded

Creating crystalline porous materials with large pores is typically challenging due to undesired interpen-etration, staggered stacking, or weakened framework stability. Here, we report a pore size expansion strategy by self-recognizing π-π stacking interactions in a series of two-dimensional (2D) hydrogen–bonded organic frameworks (HOFs), HOF-10x (x=0,1,2), self-assembled from pyrene-based tectons with systematic elongation of π-conjugated molecular arms. This strategy successfully avoids interpene-tration or staggered stacking and expands the pore size of HOF materials to access mesoporous HOF-102, which features a surface area of ~ 2,500 m2/g and the largest pore volume (1.3 cm3/g) to date among all reported HOFs. More importantly, HOF-102 shows significantly enhanced thermal and chemical stability as evidenced by powder x-ray diffraction and N2 isotherms after treatments in chal-lenging conditions. Such stability enables the adsorption of dyes and cytochrome c from aqueous media by HOF-102 and affords a processible HOF-102/fiber composite for the efficient photochemical detox-ification of a mustard gas simulant.

X-ray Crystal Structure of Gallium Tris- (8-hydroxyquinoline):  Intermolecular π−π Stacking Interactions in the Solid State

1999 ◽  
Vol 11 (3) ◽  
pp. 530-532 ◽  
Author(s):  
Yue Wang ◽  
Weixing Zhang ◽  
Yanqin Li ◽  
Ling Ye ◽  
Guangdi Yang
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Stacking Interactions ◽  
X Ray ◽  
Π Stacking

Syntheses, Spectroscopy And Crystal Structures Of (R)-N-(1-Aryl-Ethyl)Salicylaldimines And [Rh{(R)-N-(1-Aryl-Ethyl)Salicylaldiminato}(η4-Cod)] Complexes

2007 ◽  
Vol 62 (6) ◽  
pp. 807-817 ◽  
Author(s):  
Mohammed Enamullah ◽  
A.K.M. Royhan Uddin ◽  
Anne-Christine Chamayou ◽  
Christoph Janiak
Keyword(s):  
Mass Spectrometry ◽  
Schiff Base ◽  
Schiff Bases ◽  
Structure Determination ◽  
Chelate Ring ◽  
Optical Rotation ◽  
X Ray ◽  
Mononuclear Complexes ◽  
Chiral Schiff Base ◽  
C Nmr

Condensation of salicylaldehyde with enantiopure (R)-(1-aryl-ethyl)amines yields the enantiopure Schiff bases (R)-N-(1-aryl-ethyl)salicylaldimine (HSB*; aryl = phenyl, 2-methoxyphenyl, 3- methoxyphenyl, 4-methoxyphenyl (4), 4-bromophenyl (5), 2-naphthyl). These Schiff bases readily react with dinuclear (acetato)(η4-cycloocta-1,5-diene)rhodium(I), [Rh(μ-O2CMe)(η4-cod)]2, to afford the mononuclear complexes, cyclooctadiene-((R)-N-(1-aryl-ethyl)salicylaldiminato-κ2N,O)- rhodium(I), [Rh(SB∗)(η4-cod)] (SB* = deprotonated chiral Schiff base = salicylaldiminate; aryl = phenyl (7), 2-methoxyphenyl, 4-methoxyphenyl, 4-bromophenyl, 2-naphthyl). The complexes have been characterized by IR, UV/vis, 1H/13C NMR and mass spectrometry, optical rotation as well as by single-crystal X-ray structure determination for 4, 5 and 7. The structure of 5 shows C-Br· · ·π contacts. Compound 7 is only the second example of a Rh(η4-cod) complex with a six-membered Rh-N,O-chelate ring

Induction of Λ-helicity in a zinc complex with an alanine-appended aminopyridine ligand

2021 ◽  
Vol 77 (8) ◽  
Author(s):  
Berislav Perić ◽  
Zoran Kokan ◽  
Srećko I. Kirin
Keyword(s):  
Zinc Complex ◽  
Chelate Ring ◽  
Ionic Interactions ◽  
Stacking Interactions ◽  
Neutral Ligand ◽  
X Ray Diffraction ◽  
X Ray ◽  
The Third ◽  
Membered Chelate Ring ◽  
The Stability

The crystal structure of tris[dimethyl 5-({1-[(pyridin-2-yl-κN)carbamoyl-κO]ethyl}carbamoyl)benzene-1,3-dicarboxylate]zinc(II) dinitrate acetonitrile trisolvate, [Zn(C19H19N3O6)3](NO3)2·3CH3CN or [Zn(L)3](NO3)2·3CH3CN, (1), has been determined by single-crystal X-ray diffraction. The neutral ligand L coordinates to the Zn2+ cation in a bidentate fashion via the pyridine N atom and an amide O atom, forming a six-membered chelate ring. The Λ-helical chirality of the Zn2+ coordination sphere is induced by pendant L-alanine residues through stacking interactions between the arene groups of two coordinated ligands, assisted by a hydrogen bond between amide groups bonded to the stacked arene rings. The third ligand is coordinated to the Zn2+ cation by the same six-membered chelate ring, but in the opposite direction with respect to the analogous chelate rings of the first two coordinated ligands. Besides ionic interactions between [ZnL 3]2+ complexes and NO3 − anions, several types of hydrogen bonds and intermolecular stacking interactions contribute to the stability of the solid-state phase.

scholarly journals Novel Cd (II) Coordination Polymers Afforded with EDTA or Trans-1,2-Cdta Chelators and Imidazole, Adenine, or 9-(2-Hydroxyethyl) Adenine Coligands

Crystals ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 391
Author(s):  
Jeannette Carolina Belmont-Sánchez ◽  
María Eugenia García-Rubiño ◽  
Antonio Frontera ◽  
Antonio Matilla-Hernández ◽  
Alfonso Castiñeiras ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Coordination Polymers ◽  
Density Functional ◽  
Molecular Electrostatic Potential ◽  
Aqua Ligand ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Mixed Ligands

Three mixed-ligands of Cd(II) coordination polymers were unintentionally obtained: {[Cd(µ3-EDTA)(Him)·Cd(Him)(H2O)2]·H2O}n (1), {[Cd(µ4-CDTA)(Hade)·Cd(Hade)2]}n (2), and {[Cd(µ3-EDTA)(H2O)·Cd(H9heade)(H2O)]·2H2O}n (3), having imidazole (Him), adenine (Hade) or 9-(2-hydroxyethyl)adenine (9heade) as the N-heterocyclic coligands. Compounds 2 and 3 were obtained by working with an excess of corresponding N-heterocyclic coligands. The single-crystal X-ray diffraction structures and thermogravimetric analyses are reported. The chelate moieties in all three compounds exhibit hepta-coordinated Cd centers, whereas the non-chelated Cd center is five-coordinated in 1 and six-coordinated in 2 and 3. Him and Hade take part in the seven-coordinated chelate moieties in 1 and 2, respectively. In contrast, 9heade is unable to replace the aqua ligand of the chelate [Cd (EDTA) (H2O)] moiety in 3. The thermogravimetric analysis (TGA) behavior of [Cd (H2EDTA) (H2O)]·2H2O in 1 and 3 leads to a residue of CdO, whereas the N-rich compound 2 yields CdO·Cd(NO3)2 as a residue. Density functional theory (DFT) calculations along with molecular electrostatic potential (MEP) and quantum theory of atoms-in-molecules computations were performed in adenine (compound 2) and (2-hydroxyethyl)adenine (compound 3) to analyze how the strength of the H-bonding and π-stacking interactions, respectively, are affected by their coordination to the Cd-metal center.

The Syntheses and Structures of Two New Zn(II) Complexes Based on 3-Nitrobenzoato Ligand

2013 ◽  
Vol 807-809 ◽  
pp. 2671-2674
Author(s):  
Ying Bing Lu ◽  
Fang Mei Jian ◽  
Shuang Jin
Keyword(s):  
Single Crystal ◽  
Coordination Polymers ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Face To Face ◽  
Π Interactions ◽  
Carboxylate Groups ◽  
Supramolecular Chain ◽  
Supramolecular Layer

Two new Zn (II) coordination polymers with 3-nitrobenzoato ligands have been prepared, and their structures have been characterized by single-crystal X-ray diffraction techniques. The structure of [Zn (3-nbz)2(μ-4,4'-bpy)]n(1) (3-nbz = 3-nitrobenzoato, 4,4'-bpy = 4,4'-bipyridine) shows 1-D chains originating from terminal 3-nbz ligands andμ-4,4'-bpy molecules. The chains are further connected through face-to-face π stacking interactions to genenate a 2-D supramolecular layer. In Zn (3-nbz)2(2,2'-bpy) (2) (2,2'-bpy = 2,2'-bipyridine), carboxylate groups exhibit chelated bidentate to give discrete mononuclear units, which are linked by face-to-face π-π and C-H···π interactions to produce a 1-D supramolecular chain.

Coordination Polymers with a Bulky Perylene-Based Tetracarboxylate Ligand: Syntheses, Crystal Structures, and Luminescent Properties

2010 ◽  
Vol 63 (3) ◽  
pp. 463 ◽  
Author(s):  
Chun-Sen Liu ◽  
Min Hu ◽  
Song-Tao Ma ◽  
Qiang Zhang ◽  
Li-Ming Zhou ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Three Dimensional ◽  
Luminescent Properties ◽  
Supramolecular Interactions ◽  
Polymeric Chain ◽  
Stacking Interactions ◽  
One Dimensional ◽  
Π Stacking ◽  
Higher Dimensional ◽  
Interchain Interactions

To explore the coordination possibilities of perylene-based ligands with a larger conjugated π-system, four ZnII, MnII, and CoII coordination polymers with perylene-3,4,9,10-tetracarboxylate (ptc) and the chelating 1,10-phenanthroline (phen) ligands were synthesized and characterized: {[Zn2(ptc)(phen)2](H2O)10}∞ (1), {[Zn3(ptc)(OH)2(phen)2](H2O)3}∞ (2), {[Mn(ptc)0.5(phen)(H2O)2](H2O)1.5}∞ (3), and {[Co(ptc)0.5(phen)(H2O)2](H2O)2.5}∞ (4). Structural analysis reveals that complexes 1 and 2 both take one-dimensional polymeric chain structures with dinuclear and trinuclear units as nodes, respectively, which are further extended via the accessorial secondary interchain interactions, such as C–H···O H-bonding or aromatic π···π stacking interactions, to give rise to the relevant higher-dimensional frameworks. Compound 3 has a two-dimensional sheet structure that is further assembled to form a three-dimensional framework by interlayer π···π stacking interactions. Complex 4 is a one-dimensional ribbon-like array structure that is interlinked by the co-effects of intermolecular π···π stacking and C–H···π supramolecular interactions, resulting in a higher-dimensional framework from the different crystallographic directions. Moreover, complexes 1–4 exhibit strong solid-state luminescence emissions at room temperature, which mainly originate from intraligand π→π* transitions of ptc.

A zinc(II) coordination polymer based on a flexible bis(benzimidazole) ligand: synthesis, crystal structure and fluorescence study

2020 ◽  
Vol 75 (12) ◽  
pp. 1005-1009
Author(s):  
Geng Zhang ◽  
Xinzhao Xia ◽  
Jianhua Xu ◽  
Lixian Xia ◽  
Cong Wang ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Hydrothermal Reaction ◽  
Emission Peak ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
Fluorescence Study ◽  
One Dimensional ◽  
X Ray ◽  
Π Stacking ◽  
Solid State Fluorescence

AbstractA new one-dimensional Zn(II) coordination polymer, {[ZnCl2(BBM)]·CH3OH}n (2,2-(1,4-butanediyl)bis-1,3-benzimidazole [BBM]), has been obtained from the hydrothermal reaction of zinc chloride with the flexible bis-benzimidazole ligand BBM and characterized by single-crystal X-ray diffraction, elemental analysis, IR and UV–vis spectra. Structural analysis has revealed that the BBM ligand connects the Zn(II) atoms to form a square-wave chain, which is further extended into supramolecular layers through hydrogen bonds and π···π stacking interactions. Solid-state fluorescence investigations showed that the Zn(II) coordination polymer has an emission peak at 381 nm upon excitation at 330 nm, which is attributed to ligand-centered luminescence. It is only slightly red shifted as compared to the ligand but partially quenched due to the strong π···π stacking interactions.

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