scholarly journals Coordination Behaviour of 1-(4,2′:6′,4′′-terpyridin-4′-yl)ferrocene and 1-(3,2′:6′,3′′-terpyridin-4′-yl)ferrocene: Predictable and Unpredictable Assembly Algorithms

2017 ◽  
Vol 70 (5) ◽  
pp. 468 ◽  
Author(s):  
Y. Maximilian Klein ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Crystal Growth ◽  
Polymer Chains ◽  
Stacking Interactions ◽  
Helical Polymer ◽  
Π Stacking ◽  
Coordination Behaviour ◽  
Nitrogen Donors ◽  
Assembly Algorithms ◽  
Growth Experiments

The reaction of 1-(4,2′:6′,4″-terpyridin-4′-yl)ferrocene (2) with ZnI2 leads to [{ZnI2(2)}4·1.4MeOH·0.8H2O] which contains a discrete [4+4] metallocycle. Crystal growth experiments demonstrate that reactions of 2 with Zn(OAc)2 or CuCl2 result in the formation of single- or double-stranded 1D polymer chains, respectively, the latter facilitated by the formation of {Cu2Cl4} dinuclear nodes. While both 2 and its isomer 1-(3,2′:6′,3″-terpyridin-4′-yl)ferrocene (3) present V-shaped donor sets, rotation about interannular bonds in 3 generates flexible vectorial properties associated with limiting convergent and divergent orientations of the nitrogen donors. The synthesis and characterisation of 3 are described as are reactions of 3 with ZnCl2 or ZnBr2 which lead, respectively, to a metallosquare in [{ZnCl2(3)}4·3CHCl3·3MeOH] or a helical polymer in [{ZnBr2(3)}·MeOH]n. The tight pitch of the helix in the latter (8.7879(9) Å) is controlled by a combination of the orientations of the N,N″-donor sets in 3, and intra-chain π-stacking interactions involving ferrocenyl and pyridine units.

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.

scholarly journals catena-Poly[[[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole-κ2N1,N5](dicyanamido-κN)copper(II)]-μ2-dicyanamido-κ2N:N′]: coordination polymer chains linked into a bilayer by hydrogen bonds and π–π stacking interactions

2014 ◽  
Vol 70 (4) ◽  
pp. 359-363 ◽  
Author(s):  
Zouaoui Setifi ◽  
Fatima Setifi ◽  
Mohamed Saadi ◽  
Djamil-Azzeddine Rouag ◽  
Christopher Glidewell
Keyword(s):  
Coordination Polymer ◽  
Hydrogen Bonds ◽  
Polymer Chains ◽  
Stacking Interactions ◽  
Terminal Ligand ◽  
One Dimensional ◽  
Bridging Ligand ◽  
Pyramidal Geometry ◽  
Π Stacking ◽  
Square Pyramidal Geometry

In the title compound, [Cu(C2N3)2(C12H10N6)]nor [Cu(dca)2(abpt)]n, where abpt is 4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole and dca is the dicyanamide anion, the CuIIcentre is five-coordinate with an approximately square-pyramidal geometry. One of the two dicyanamide ligands is a terminal ligand, but the other one acts as a μ1,5-bridging ligand between pairs of CuIIcentres, so generating a one-dimensional coordination polymer. A combination of N—H...N and C—H...N hydrogen bonds, augmented by π–π stacking interactions, links the coordination polymer chains into a bilayer structure. Comparisons are made with some related CuIIcomplexes containing dca ligands and heteroaromatic co-ligands.

scholarly journals Crystal structure of a twisted-ribbon type double-stranded AgIcoordination polymer:catena-poly[[silver(I)-μ3-bis(pyridin-3-ylmethyl)sulfane-κ3N:N′:S] nitrate]

2017 ◽  
Vol 73 (10) ◽  
pp. 1587-1589 ◽  
Author(s):  
Suk-Hee Moon ◽  
Youngjin Kang ◽  
Ki-Min Park
Keyword(s):  
Three Dimensional ◽  
Polymer Chains ◽  
Zigzag Chain ◽  
Stacking Interactions ◽  
Asymmetric Unit ◽  
Parallel Chain ◽  
Π Stacking ◽  
Centroid Distance ◽  
Nitrate Anions ◽  
Coordination Plane

The asymmetric unit in the title compound, {[Ag(C12H12N2S)]·NO3}nor {[AgL]·NO3}n,L= bis(pyridin-3-ylmethyl)sulfane, consists of an AgIcation bound to a pyridine N atom of anLligand and an NO3−anion that is disordered over two orientations in an 0.570 (17):0.430 (17) occupancy ratio. Each AgIcation is coordinated by two pyridine N atoms from adjacentLligands to form an infinite zigzag chain along [110]. In addition, each AgIion binds to an S donor from a thirdLligand in an adjacent parallel chain, resulting in the formation of a twisted-ribbon type of double-stranded chain propagating along the [110] or [1-10] directions. The AgIatom is displaced out of the trigonal N2S coordination plane by 0.371 (3) Å because of interactions between the AgIcation and O atoms of the disordered nitrate anions. Intermolecular π–π stacking interactions [centroid-to-centroid distance = 3.824 (3) Å] occur between one pair of corresponding pyridine rings in the double-stranded chain. In the crystal, the double-stranded chains are alternately stacked along thecaxis with alternate stacks linked by intermolecular π–π stacking interactions [centroid-to-centroid distance = 3.849 (3) Å], generating a three-dimensional supramolecular architecture. Weak intermolecular C—H...O hydrogen bonds between the polymer chains and the O atoms of the nitrate anions also occur.

SuFExable Polymers with Helical Structures Derived from Thionyl Tetrafluoride (SOF4)

2019 ◽  
Author(s):  
Suhua Li ◽  
Gencheng Li ◽  
Bing Gao ◽  
Sidharam P. Pujari ◽  
Xiaoyan Chen ◽  
...  
Keyword(s):  
Functional Polymers ◽  
Polymer Chains ◽  
New Materials ◽  
Helical Structures ◽  
Polymer Backbone ◽  
Silyl Ethers ◽  
Helical Polymer ◽  
Key Characteristics ◽  
Post Modification ◽  
Individual Polymer

The first SuFEx click chemistry synthesis of SOF<sub>4</sub>-derived copolymers based upon the polymerization of bis(iminosulfur oxydifluorides) and bis(aryl silyl ethers) is described. This novel class of SuFEx polymer presents two key characteristics: First, the newly created [-N=S(=O)F-O-] polymer backbone linkages are themselves SuFExable and primed to undergo further high-yielding and precise SuFEx-based post-modification with phenols or amines to yield branched functional polymers. Second, studies of individual polymer chains of several of these new materials indicate the presence of helical polymer structures, which itself suggests a preferential approach of new monomers onto the growing polymer chain upon the formation of the stereogenic linking moiety.

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.

Examination of Aggregation Induced Enhanced Emission in a Propeller Shaped Chiral- Nonconjugated Blue Emitter from Restricted Intramolecular Rotation and J Type π⋯π Stacking Interactions

2021 ◽  
Author(s):  
Gul Yakali
Keyword(s):  
Thin Film ◽  
Small Molecules ◽  
Solid Phase ◽  
Stacking Interactions ◽  
Optoelectronic Materials ◽  
Π Stacking ◽  
Intramolecular Rotation

Fluorescent organic small molecules with the property of aggregation induced enhanced emission in the solid phase (crystall or thin film) have great attention for the design of optoelectronic materials. Generally,...

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

A macrocyclic [60]fullerene–porphyrin dyad involving π–π stacking interactions

1998 ◽  
pp. 1981-1982 ◽  
Author(s):  
Elke Dietel ◽  
Andreas Hirsch ◽  
Emerich Eichhorn ◽  
Anton Rieker ◽  
Steffen Hackbarth ◽  
...  
Keyword(s):  
Stacking Interactions ◽  
Π Stacking

scholarly journals Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu2(μ-OAc)4(3,2′:6′,3″-tpy)]n 1D-Polymers

Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 182-198
Author(s):  
Dalila Rocco ◽  
Samantha Novak ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Metal Binding ◽  
Polymer Chains ◽  
X Ray Diffraction ◽  
Face To Face ◽  
Single Crystal Structures ◽  
Π Stacking ◽  
Metal Binding Domain ◽  
Packing Interactions

We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (1), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (2), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (3), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (4), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (5), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu2(μ-OAc)4L]n 1D-coordination polymers with L = 1–5 have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in 1 by an F substituent in 2 has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for 1 or H...F for 2) are only secondary packing interactions. Upon going from [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n to [Cu2(μ-OAc)4(3)]n, [Cu2(μ-OAc)4(4)]n, and [Cu2(μ-OAc)4(5)]n·nMeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility.

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