The terpyridine isomer game: from chelate to coordination network building block

Housecroft, Catherine E.; Constable, Edwin C.

doi:10.1039/d0cc04477f

Cited by 36 publications

(52 citation statements)

References 71 publications

(58 reference statements)

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“…tpybased molecules have been extensively studied since the 1930s, however, it is worth noting that the unique structure of MB, has never been reported. 40,[63][64] The synthesis of MB (yield 75%) and selfassembly of complex Zn 3 (MB) 2 (yield 87%) (MB:Zn(II)=2:3) followed the same procedure as that of Self-sorting behavior of MA, MB, and tpy. To evaluate the selectivity of these model systems, we investigated the self-sorting behavior of MA, MB, and conventional tpy.…”

Section: Synthesis and Characterization Of Model System Mb And Complex Zn 3 (Mb)mentioning

confidence: 99%

Designing Narcissistic Self-Sorting Terpyridine Moieties with High Coordination Selectivity for Complex Metallo-Supramolecules

Duan

et al. 2021

Preprint

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Coordination-driven self-assembly serves as a powerful approach for the construction of metallo-supramolecules, however, it still remains its infancy in design of coordination moieties with high selectivity and specificity. Herein, two unique ortho-modified terpyridine ligands (MA and MB) were designed and synthesized to form head-to-tail coordination complexes with Zn(II) respectively. Both of them showed excellent narcissistic self-sorting process due to the exquisite design. Further, two multitopic ligands (LA and LB) with narcissistic self-sorting moieties were obtained and used to construct more complex metallo-supramolecules hexagons. More interestingly, because of the non-coaxial structural restrictions in the rotation of terpyridine moieties, the obtained hexagonal macrocycles were able to hierarchically self-assemble into giant cyclic nanostructures via side-to-side stacking rather than face-to-face stacking. Our design of dissymmetrical coordination moieties could pave a new avenue for the development of congested coordination pairs with high selectivity and specificity.

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Section: Synthesis and Characterization Of Model System Mb And Complex Zn 3 (Mb)mentioning

confidence: 99%

Designing Narcissistic Self-Sorting Terpyridine Moieties with High Coordination Selectivity for Complex Metallo-Supramolecules

Duan

et al. 2021

Preprint

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“…Ditopic bis(tpy) ligands designed to assemble metallomacrocycles with predetermined internal angles feature in the innovative work of Newkome and coworkers [7]. However, while retaining a terpyridine building block, the most efficient way to access 1Dcoordination polymers and 2D-and 3D-coordination networks is to turn to other isomers of terpyridine [8]. The 4,2 :6 ,4 -and 3,2 :6 ,3 -isomers are synthetically accessible using either Kröhnke methodology [9] or the one-pot approach of Wang and Hanan [10].…”

Section: Introductionmentioning

confidence: 99%

“…The 4,2 :6 ,4 -and 3,2 :6 ,3 -isomers are synthetically accessible using either Kröhnke methodology [9] or the one-pot approach of Wang and Hanan [10]. Over the last decade, the coordination chemistry of 4,2 :6 ,4 -terpyridines (4,2 :6 ,4 -tpy (I), Scheme 1) has gained in popularity [8]. Functionalization in the 4 -position with coordinatively noninnocent substituents increases the connectivity of the building block, taking it from a V-shaped linker to a 3-(or higher) connecting node.…”

Section: Introductionmentioning

confidence: 99%

“…Functionalization in the 4 -position with coordinatively noninnocent substituents increases the connectivity of the building block, taking it from a V-shaped linker to a 3-(or higher) connecting node. It is noteworthy that the introduction The coordination chemistry of 3,2′:6′,3″-tpy has received less attention than that of the 4,2′:6′,4"-isomer [8]. One aspect of 3,2′:6′,3″-tpy that makes predictive crystal engineering difficult is that rotation about the inter-ring C-C bonds (Scheme 2) leads to different ligand conformations and, therefore, to variable vectorial properties of the ditopic ligand.…”

Section: Introductionmentioning

confidence: 99%

“…The same is true in 3,2′:6′,3″-terpyridine (3,2′:6′,3″-tpy). The coordination chemistry of 3,2′:6′,3″-tpy has received less attention than that of the 4,2′:6′,4"-isomer [8]. One aspect of 3,2′:6′,3″-tpy that makes predictive crystal engineering difficult is that rotation about the inter-ring C-C bonds (Scheme 2) leads to different ligand conformations and, therefore, to variable vectorial properties of the ditopic ligand.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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Terpyridine‐Based 3D Metal–Organic‐Frameworks: A Structure–Property Correlation

Elahi

Raizada

Sahu

et al. 2021

Chemistry A European J

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Design, synthesis, and applications of metal–organic frameworks (MOFs) are among the most salient fields of research in modern inorganic and materials chemistry. As the structure and physical properties of MOFs are mostly dependent on the organic linkers or ligands, the choice of ligand system is of utmost importance in the design of MOFs. One such crucial organic linker/ligand is terpyridine (tpy), which can adopt various coordination modes to generate an enormous number of metal–organic frameworks. These frameworks generally carry physicochemical characteristics induced by the π‐electron‐rich (basically N‐electron‐rich moiety) terpyridines. In this minireview, the construction of 3D MOFs associated with symmetrical terpyridines is discussed. These ligands can be easily derivatized at the lateral phenyl (4′‐phenyl) position and incorporate additional organic functionalities. These functionalities lead to some different binding modes and form higher dimensional (3D) frameworks. Therefore, these 3D MOFs can carry multiple features along with the characteristics of terpyridines. Some properties of these MOFs, like photophysical, chemical selectivity, photocatalytic degradation, proton conductivity, and magnetism, etc. have also been discussed and correlated with their frameworks.

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The terpyridine isomer game: from chelate to coordination network building block

Abstract: The first 4,2':6',4"-terpyridine (4,2':6',4"-tpy) containing coordination polymer was reported over 20 years ago and in the last decade, there has been increased interest in the use of ditopic 4,2':6',4"-tpy ligands...

Cited by 36 publications

References 71 publications

Designing Narcissistic Self-Sorting Terpyridine Moieties with High Coordination Selectivity for Complex Metallo-Supramolecules

Designing Narcissistic Self-Sorting Terpyridine Moieties with High Coordination Selectivity for Complex Metallo-Supramolecules

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

Terpyridine‐Based 3D Metal–Organic‐Frameworks: A Structure–Property Correlation

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