Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

Constable, Edwin C.; Housecroft, Catherine E.

doi:10.1016/b978-0-08-097774-4.00823-8

Cited by 3 publications

(4 citation statements)

References 203 publications

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“…The coordinating groups may on the one hand differ in their Pearson hardness allowing preferred interaction with matching metal cations. , Alternatively, coordinating groups can be selectively activated by deprotonation. A combination of both approaches can further increase site selectivity. − A popular route to synthesize these heterometallic CPs is by sequential addition of the metal cations. − The reaction with the first metal cation yields an intermediate commonly referred to as a metalloligand. , The other coordinating group of the ligand is free to react with the second cation. − …”

Section: Introductionmentioning

confidence: 99%

A Rigid Linker for Site-Selective Coordination of Transition Metal Cations: Combining an Acetylacetone with a Caged Phosphine

et al. 2023

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The combination of a soft phosphorus and a hard oxygen donor in the new ligand HacacTRIP leads to excellent site selectivity for the coordination of two different metal cations of matching Pearson character. The deprotonation step required for coordinating the acetylacetone oxygen donor further increases the selectivity. In contrast to most phosphines, the use of the caged phosphatriptycene motif enables a rigid and directional orientation of the phosphorus binding site which is required to form stable coordination network structures. In addition to the synthesis of HacacTRIP, we present its selective coordination. The deprotonated acetylacetone was selectively bound to CuII and FeIII. The solid state structure of the former displays a rare axial coordination of chloroform molecules. The phosphorus donor was selectively coordinated to the monovalent coinage metal cations CuI, AgI, and AuI. The CuI and AgI complexes represent the first examples in which a phosphatriptycene is bound to these metal cations. Heterometallic coordination compounds were characterized with combinations of these two groups. They comprise an oligonuclear CuI/CuII mixed-valence compound in which iodide binds to both CuI and CuII cations and a complex in which acacTRIP– bridges CuII and AuI. In addition to these discrete aggregates, the ligand has been used to link FeIII and AgI into a 2D coordination polymer with unprecedented trigonal planar coordination of three bulky phosphatriptycenes to a cation and resulting honeycomb topology. Its almost regular hexagons underline the desired rigidity of the ditopic acacTRIP– ligand.

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Section: Introductionmentioning

confidence: 99%

A Rigid Linker for Site-Selective Coordination of Transition Metal Cations: Combining an Acetylacetone with a Caged Phosphine

et al. 2023

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“…If a porous material is desired, the geometry between the coordination sites should be sufficiently rigid to support the pores upon desolvation. [23][24][25] While the ligands designed for polymers with a single type of metal cation mostly exhibit multiple copies of the same coordination site, e.g. in 4,4′-bipyridine, 13,26 the selective coordination of two different metal cations is most often achieved by using heteropolytopic ligands with at least two distinctly different coordination sites with a discrepancy in their respective Pearson hardness.…”

Section: Introductionmentioning

confidence: 99%

“…If a porous material is desired, the geometry between the coordination sites should be sufficiently rigid to support the pores upon desolvation. 23–25…”

Section: Introductionmentioning

confidence: 99%

Phosphorus or nitrogen – the first phosphatriptycene in coordination polymer chemistry

et al. 2022

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“…To date, there are no examples in which the central pyridine ring coordinates to a metal center. On the one hand, the outcome of the assembly process with 4,2′:6′,4″- and 3,2′:6′,3″-tpy ligands is less predictable than with a linear rigid-rod such as 4,4′-bipyridine [ 4 , 5 ]. This is particularly true for 3,2′:6′,3″-tpy, where the conformational flexibility leads to varying vectorial dispositions of the nitrogen lone pairs ( Scheme 1 ) [ 6 , 7 ].…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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The preparation and characterization of the isomers rac-4′-(4-butan-2-yloxyphenyl)-3,2′:6′,3″-terpyridine (rac-2), 4′-(2-methylpropoxyphenyl)-3,2′:6′,3″-terpyridine (3) and 4′-(tert-butoxyphenyl)-3,2′:6′,3″-terpyridine (4) are reported. The compounds react with Co(NCS)2 under conditions of crystal growth at room temperature to give single crystals of [{Co(rac-2)2(NCS)2}·CHCl3]n, [Co(3)2(NCS)2]n and [{Co(4)2(NCS)2}·CHCl3]n which possess (4,4) networks, with the Co centers acting as 4-connecting nodes. Powder X-ray diffraction (PXRD) was used to confirm that the crystals chosen for single crystal X-ray diffraction were representative of the bulk samples. The detailed structures of the three networks have been compared with that of the previously reported [{Co(1)2(NCS)2}·4CHCl3]n in which 1 is 4′-(butoxyphenyl)-3,2′:6′,3″-terpyridine. Whereas the switch from 1 with the straight-chain butoxy substituent to rac-2, 3 and 4 with branched chains causes significant structural perturbation, changes in the spatial properties of the branched substituents are accommodated with subtle conformational changes in the 3,2′:6′,3″-tpy domain.

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Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

Cited by 3 publications

References 203 publications

A Rigid Linker for Site-Selective Coordination of Transition Metal Cations: Combining an Acetylacetone with a Caged Phosphine

A Rigid Linker for Site-Selective Coordination of Transition Metal Cations: Combining an Acetylacetone with a Caged Phosphine

Phosphorus or nitrogen – the first phosphatriptycene in coordination polymer chemistry

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

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