Straight Versus Branched Chain Substituents in 4′-(Butoxyphenyl)-3,2′:6′,3″-terpyridines: Effects on (4,4) Coordination Network Assemblies

Rocco, Dalila; Prescimone, Alessandro; Constable, Edwin C.; Housecroft, Catherine E.

doi:10.3390/polym12081823

Cited by 4 publications

(3 citation statements)

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“…We have also investigated the effects of the length of the alkyl chain in [CoL2(NCS)2]n 2Dnetworks in which L is a 4'-(4-n-alkyloxyphenyl)-3,2':6',3"-terpyridine, and have demonstrated that an increase in the n-alkyloxy chain length results in a change in the conformation of the 3,2':6',3"-tpy metal-binding domain [10]. This investigation was extended to isomeric C4-alkyloxy substituents, and revealed significant structural perturbation on going from n-butyl to branched isomers, but only subtle changes across the series rac-4-butan-2-yl, 2-methylpropyl and tert-butyl peripheral groups [21]. We have also investigated the effects of introducing different halogen-substituents in 3,2':6',3"-tpy and 4,2':6',4"-tpy ligands containing 4'-biphenyl-4-yl substituents [12,22].…”

Section: Introductionmentioning

confidence: 92%

Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines

et al. 2021

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Coordination networks formed between Co(NCS)2 and 4’-substituted-[1,1’-biphenyl]-4-yl-3,2’:6’,3”-terpyridines in which the 4’-group is Me (1), H (2), F (3), Cl (4) or Br (5) are reported. [Co(1)2(NCS)2]n.4.5nCHCl3, [Co(2)2(NCS)2]n.4.3nCHCl3, [Co(3)2(NCS)2]n.4nCHCl3, [Co(4)2(NCS)2]n, and [Co(5)2(NCS)2]n.nCHCl3 are 2D-networks directed by 4-connecting cobalt nodes. Changes in the conformation of the 3,2’:6’,3”-tpy unit coupled with the different peripheral substituents lead to three structure types. In [Co(1)2(NCS)2]n.4.5nCHCl3, [Co(2)2(NCS)2]n.4.3nCHCl3, [Co(3)2(NCS)2]n.4nCHCl3, cone-like arrangements of [1,1’-biphenyl]-4-yl units pack through pyridine...arene π-stacking, whereas Cl...π interactions are dominant in the packing in [Co(4)2(NCS)2]n. The introduction of the Br substituent in ligand 5 switches off both face-to-face π-stacking and halogen...π-interactions, and the packing interactions are more subtly controlled. Assemblies with organic linkers 1–3 are structurally similar and the lattice accommodates CHCl3 molecules in distinct cavities; thermogravimetric analysis confirmed that half the solvent in [Co(3)2(NCS)2]n.4nCHCl3 can be reversibly removed.

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Section: Introductionmentioning

confidence: 92%

Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines

et al. 2021

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“…Our recent investigations into the formation of (4,4) nets assembled from 3,2 :6 ,3 -tpy ligands and Co(NCS) 2 illustrated both the conformational flexibility of the 3,2 :6 ,3 -tpy unit (Scheme 1) and the effects of introducing different alkyloxy substituents in the 4 -position of the 3,2 :6 ,3 -tpy ligand [17][18][19]. We also noted the role that different lattice solvents play in assemblies arising from a combination of Co(NCS) 2 and 4 -{4-(naphthalen-1-yl)phenyl}-3,2 :6 ,3 -terpyridine [20].…”

Section: Introductionmentioning

confidence: 99%

To Be or Not to Be a (4,4) Net: Reactions of 4′-{4-(N,N-Diethylaminophenyl)}- and 4′-{4-(N,N-Diphenylaminophenyl)}-3,2′:6′,3″- and 4,2′:6′,4″-Terpyridines with Cobalt(II) Thiocyanate

et al. 2022

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The ligands 4′-{4-(N,N-diethylaminophenyl)}-3,2′:6′,3″-terpyridine (1) and 4′{4-(N,N-diphenylaminophenyl)}-3,2′:6′,3″-terpyridine (2) were prepared and characterized, including the single crystal structure of 2. Along with their 4,2′:6′,4″-terpyridine isomers, 3 and 4, ligands 1 and 2 were reacted with Co(NCS)2 under conditions of crystal growth by layering, using solvent mixtures of MeOH and CHCl3. The single crystal structures of [Co(NCS)2(1)]n.0.8nCHCl3, [Co(NCS)2(2)2(MeOH)2].3CHCl3, [Co(NCS)2(3)]n.2nCHCl3, and [Co(NCS)2(4)]n were determined. The complexes with 1, 3, and 4 assemble into 2D (4,4) nets with the Co(II) centres as 4-connecting nodes, whereas [Co(NCS)2(2)2(MeOH)2] is a discrete molecular species, illustrating that MeOH can act as a non-innocent solvent. The effects on the structure of changing from the 3,2′:6′,3″-terpyridine (3,2′:6′,3″-tpy) to a 4,2′:6′,4″-tpy metal-binding unit, and of introducing R2N functionalities with different steric demands, are discussed. PXRD of bulk samples of all four products confirmed the single-crystal structures as representative of the bulk materials.

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“…Scheme 2 illustrates the three possible planar conformations of 3,2 :6 ,3 -tpy. We have recently demonstrated conformational switching in free 4 -(4-n-alkyloxyphenyl)-3,2 :6 ,3 -terpyridines [12], and in [Cu 2 (µ-OAc) 4 L] n 1D-chains [13] and [Co(NCS) 2 L 2 ] n 2D-networks where L is a 4 -(4-n-alkyloxyphenyl)-3,2 :6 ,3 -tpy [14,15] as a function of the alkyloxy chain length. In these structures, the 3,2 :6 ,3 -tpy domain adopts either conformation I or II (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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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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Straight Versus Branched Chain Substituents in 4′-(Butoxyphenyl)-3,2′:6′,3″-terpyridines: Effects on (4,4) Coordination Network Assemblies

Cited by 4 publications

References 36 publications

Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines

Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines

To Be or Not to Be a (4,4) Net: Reactions of 4′-{4-(N,N-Diethylaminophenyl)}- and 4′-{4-(N,N-Diphenylaminophenyl)}-3,2′:6′,3″- and 4,2′:6′,4″-Terpyridines with Cobalt(II) Thiocyanate

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

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