What a difference a tail makes: 2D → 2D parallel interpenetration of sheets to interpenetrated <b>nbo</b> networks using ditopic-4,2′:6′,4′′-terpyridine ligands

Klein, Y. Maximilian; Prescimone, Alessandro; Neuburger, Markus; Constable, Edwin C.; Housecroft, Catherine E.

doi:10.1039/c7ce00686a

Cited by 16 publications

(25 citation statements)

References 49 publications

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“…The synthetic route to 8 is summarized in Scheme 3 and is closely related to the synthesis of 2 [15]. Compound 8a (Scheme 3) was prepared from the commercially available 2,5-dibromohydroquinone and then reacted with n BuLi followed by DMF to yield the dialdehyde 8b .…”

Section: Resultsmentioning

confidence: 99%

“…We have demonstrated that the length of such tails can have a significant impact on the outcome of assembly processes [13,14,15]. Single crystals grown by layering a MeOH solution of Co(NCS) 2 over a CHCl 3 solution of 8 were not of X-ray quality.…”

Section: Resultsmentioning

confidence: 99%

“…Rotation about the C–spacer bonds permits the node to have limiting planar or approximately tetrahedral geometries, and the directionality of the assembly can be modified by switching from 4,2’:6’,4”-tpy to 3,2’:6’,3”-tpy domains. We have recently employed such ditopic ligands in which the spacer (Scheme 1c) is a 1,4-C 6 H 4 ring to assemble parallel interpenetrating 2D→2D sheets [13,14,15] and 3D-metal-organic frameworks (MOFs) [15,16]. Going to a ferrocen-1,1’-yl spacer introduces rotational freedom and, in [{Zn 2 ( 1 )Cl 4 }∙3CHCl 3 ] n where 1 = 1,1’-bis(4,2’:6’,4”-terpyridin-4’-yl)ferrocene (Scheme 2), the ligand adopts a cisoid-conformation, leading to a double-stranded 1D-polymer chain [17].…”

Section: Introductionmentioning

confidence: 99%

“…However, the choice of metal is naturally important since its preferred coordination number and geometry dictate whether it will act as a linker or node. When connected through ZnX 2 units (X = halide) as in [Zn 2 Br 4 ( 2 )∙H 2 O] n ( 2 is shown in Scheme 2), ligand 2 acts as a 4-connecting node and the zinc(II) atoms are linkers; the assembly is a MOF consisting of 2-fold interpenetrating nbo nets [15]. In contrast, when ligand 3 (Scheme 2) is combined with Co(NCS) 2 , both the metal and ligand function as 4-connecting nodes (planar and approximately tetrahedral, respectively) and assemble into a 3D {4 2 .8 4 } lvt net [16].…”

Section: Introductionmentioning

confidence: 99%

“…A feature that the ferrocenyl unit in 1 or 7 brings to crystal packing is its possibility for face-to-face π-stacking with pyridine rings [24]. Ditopic ligand 8 (Scheme 3) is a member of the 1,4-bis(alkoxy)-2,5-bis(4,2’:6’,4”-terpyridin-4’-yl)benzene family to which 2 (Scheme 2) belongs; while we have investigated assemblies formed between such ligands with zinc(II) halides [15], we have not described reactions with Co(NCS) 2 . Finally, ligand 9 (Scheme 3) is analogous to 3 in terms of the four N -donors.…”

Section: Introductionmentioning

confidence: 99%

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4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

et al. 2017

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A comparative investigation of the coordination assemblies formed between Co(NCS)2 and two monotopic 4,2’:6’,4’’-terpyridine (4,2’:6’,4”-tpy) ligands or two related ditopic ligands is reported. Crystals were grown by layering MeOH solutions of Co(NCS)2 over a CHCl3 or 1,2-C6H4Cl2 solution of the respective ligand at room temperature. With 4’-(2-methylpyrimidin-5-yl)-4,2’:6’,4”-terpyridine (6), the 1D-coordination polymer {[Co2(NCS)4(MeOH)4(6)2]∙2MeOH∙8H2O}n assembles with 6 coordinating only through the outer N-donors of the 4,2’:6’,4”-tpy unit; coordination by the MeOH solvent blocks two cobalt coordination sites preventing propagation in a higher-dimensional network. A combination of Co(NCS)2 and 1-(4,2‘:6’,4”-terpyridin-4’-yl)ferrocene (7) leads to {[Co(NCS)2(7)2]∙4CHCl3}n which contains a (4,4) net; the 2D-sheets associate through π-stacking interactions between ferrocenyl and pyridyl units. A 3D-framework is achieved through use of the ditopic ligand 1,4-bis(npropoxy)-2,5-bis(4,2’:6’,4”-terpyridin-4’-yl)benzene (8) which acts as a 4-connecting node in {[Co(NCS)2(8)2]∙2C6H4Cl2}n; the combination of metal and ligand planar 4-connecting nodes results in a {65.8} cds net. For a comparison with the coordinating abilities of the previously reported 1,4-bis(noctoxy)-2,5-bis(4,2’:6’,4”-terpyridin-4’-yl)benzene (3), a more flexible analogue 9 was prepared. {[Co(NCS)2(9)]∙2CHCl3}n contains a (4,4) net defined by both metal and ligand planar 4-connecting nodes. The noctoxy tails of 9 protrude from each side of the (4,4) net and thread through adjacent sheets; the arene-attached noctoxy chains associate through a combination of van der Waals and C–H...π interactions.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

et al. 2017

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Does the Central Nitrogen Atom Make a Difference? A Comparison of Non‐Coordinating Pyridine and Benzene Spacers in Multitopic Ligands

Housecroft,

Constable

2024

Helvetica Chimica Acta

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In metal coordination compounds of the divergent ligands 4,2':6',4"‐terpyridine and 3,2':6',3"‐terpyridine and their 4'‐functionalized derivatives, the central pyridine ring of the 4,2':6',4"‐terpyridine and 3,2':6',3"‐terpyridine domains is non‐coordinated. We present an overview of data from the Cambridge Structural Database to assess whether there are structural similarities between the coordination compounds of 4,2':6',4"‐tpy and 1,3‐di(pyridin‐4‐yl)benzene, and between 3,2':6',3"‐tpy and 1,3‐di(pyridin‐3‐yl)benzene. Based upon structurally characterized compounds, it emerges that the coordination chemistry of ligands including one or more 4,2':6',4"‐terpyridine or 3,2':6',3"‐terpyridine metal‐binding domains dominate over those of corresponding ligands based upon 1,3‐di(pyridin‐4‐yl)benzene and 1,3‐di(pyridin‐3‐yl)benzene. We provide an overview of metallamacrocycles and cages, 1D‐coordination polymers and 2D‐ and 3D‐networks

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Tetratopic bis(4,2′:6′,4′′-terpyridine) and bis(3,2′:6′,3′′-terpyridine) Ligands as 4-Connecting Nodes in 2D-Coordination Networks and 3D-Frameworks

Housecroft

Constable

2017

J Inorg Organomet Polym

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Ditopic, 4,2':6',4''-terpyridine (4,2':6',4''-tpy) and 3,2':6',3''-terpyridine (3,2':6',3''-tpy) present a divergent N,N'-donor set (the central N atom typically being non-coordinated) and are ideal building blocks for the assembly of coordination polymers and networks. The step from ditopic to tetratopic ligands which contain two interconnected 4,2':6',4''-tpy or 3,2':6',3''-tpy metal-binding domains renders the ligand capable of acting as a 4-connecting node and is a successful route to increasing the dimensionality of the assembly. In this short overview, we illustrate the recent development of the use of bis(4,2':6',4''-tpy) and bis(3,2':6',3''-tpy) ligands and compare strategies using either ditopic or tetratopic ligands.

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What a difference a tail makes: 2D → 2D parallel interpenetration of sheets to interpenetrated nbo networks using ditopic-4,2′:6′,4′′-terpyridine ligands

Cited by 16 publications

References 49 publications

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

Does the Central Nitrogen Atom Make a Difference? A Comparison of Non‐Coordinating Pyridine and Benzene Spacers in Multitopic Ligands

Tetratopic bis(4,2′:6′,4′′-terpyridine) and bis(3,2′:6′,3′′-terpyridine) Ligands as 4-Connecting Nodes in 2D-Coordination Networks and 3D-Frameworks

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