Interpenetration in π-rich mixed-ligand coordination polymers

Stephanie Boer, David Turner

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Structural and chemical influences on interpenetration have been investigated through the preparation and structural analysis of a series of seven chiral coordination polymers using a phenylalanine-substituted naphthalenediimide ligand (H2PheNDI). The reaction of H2PheNDI with MnII or CdII and a range of linear dipyridyl-based coligands forms a series of coordination polymers which vary greatly in terms of their topologies and interpenetration while largely retaining a common metallomacrocyclic motif. The metallomacrocyclic motif is found in a tube-like 1D coordination polymer poly-[Cd(bipy)(OH2)(PheNDI)] (2) and a closely related 2D polythreaded network poly-{[Cd2(bipy)2(PheNDI)2][Cd(bipy)(DMF)1.5(NO3)2(OH2)0.5]} (3) which are synthesized as pure phases under slightly different conditions. The longer 1,2-di(4-pyridyl)ethylene (dpe) ligand gives rise to a 2D coordination polymer poly-[Cd4(DMF)(dpe)4(OH2)2(PheNDI)4] (5) in which the metallomacrocycles are connected only "sideways" rather than as a tube. This difference allows for 2-fold 2D → 2D interpenetration, between two crystallographically distinct sheets, whereby the dpe passes through the metallomacrocycle, assisted by face-to-face aromatic interactions. The use of a larger dipyridyl ligand, N,N′-bis(4-pyridyl)naphthalenediimide (4pyNDI), yielded 3D coordination polymers with distorted pcu topologies of the form poly-[M2(PheNDI)2(4PyNDI)2] (M = Cd, 6; Mn, 7) which contain neither the metallomacrocyclic motif nor interpenetration.

Original languageEnglish
Pages (from-to)6294-6303
Number of pages10
JournalCrystal Growth and Design
Volume16
Issue number11
DOIs
Publication statusPublished - 2 Nov 2016

Cite this

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title = "Interpenetration in π-rich mixed-ligand coordination polymers",
abstract = "Structural and chemical influences on interpenetration have been investigated through the preparation and structural analysis of a series of seven chiral coordination polymers using a phenylalanine-substituted naphthalenediimide ligand (H2PheNDI). The reaction of H2PheNDI with MnII or CdII and a range of linear dipyridyl-based coligands forms a series of coordination polymers which vary greatly in terms of their topologies and interpenetration while largely retaining a common metallomacrocyclic motif. The metallomacrocyclic motif is found in a tube-like 1D coordination polymer poly-[Cd(bipy)(OH2)(PheNDI)] (2) and a closely related 2D polythreaded network poly-{[Cd2(bipy)2(PheNDI)2][Cd(bipy)(DMF)1.5(NO3)2(OH2)0.5]} (3) which are synthesized as pure phases under slightly different conditions. The longer 1,2-di(4-pyridyl)ethylene (dpe) ligand gives rise to a 2D coordination polymer poly-[Cd4(DMF)(dpe)4(OH2)2(PheNDI)4] (5) in which the metallomacrocycles are connected only {"}sideways{"} rather than as a tube. This difference allows for 2-fold 2D → 2D interpenetration, between two crystallographically distinct sheets, whereby the dpe passes through the metallomacrocycle, assisted by face-to-face aromatic interactions. The use of a larger dipyridyl ligand, N,N′-bis(4-pyridyl)naphthalenediimide (4pyNDI), yielded 3D coordination polymers with distorted pcu topologies of the form poly-[M2(PheNDI)2(4PyNDI)2] (M = Cd, 6; Mn, 7) which contain neither the metallomacrocyclic motif nor interpenetration.",
author = "Stephanie Boer and David Turner",
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Interpenetration in π-rich mixed-ligand coordination polymers. / Boer, Stephanie; Turner, David.

In: Crystal Growth and Design, Vol. 16, No. 11, 02.11.2016, p. 6294-6303.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Interpenetration in π-rich mixed-ligand coordination polymers

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AU - Turner, David

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N2 - Structural and chemical influences on interpenetration have been investigated through the preparation and structural analysis of a series of seven chiral coordination polymers using a phenylalanine-substituted naphthalenediimide ligand (H2PheNDI). The reaction of H2PheNDI with MnII or CdII and a range of linear dipyridyl-based coligands forms a series of coordination polymers which vary greatly in terms of their topologies and interpenetration while largely retaining a common metallomacrocyclic motif. The metallomacrocyclic motif is found in a tube-like 1D coordination polymer poly-[Cd(bipy)(OH2)(PheNDI)] (2) and a closely related 2D polythreaded network poly-{[Cd2(bipy)2(PheNDI)2][Cd(bipy)(DMF)1.5(NO3)2(OH2)0.5]} (3) which are synthesized as pure phases under slightly different conditions. The longer 1,2-di(4-pyridyl)ethylene (dpe) ligand gives rise to a 2D coordination polymer poly-[Cd4(DMF)(dpe)4(OH2)2(PheNDI)4] (5) in which the metallomacrocycles are connected only "sideways" rather than as a tube. This difference allows for 2-fold 2D → 2D interpenetration, between two crystallographically distinct sheets, whereby the dpe passes through the metallomacrocycle, assisted by face-to-face aromatic interactions. The use of a larger dipyridyl ligand, N,N′-bis(4-pyridyl)naphthalenediimide (4pyNDI), yielded 3D coordination polymers with distorted pcu topologies of the form poly-[M2(PheNDI)2(4PyNDI)2] (M = Cd, 6; Mn, 7) which contain neither the metallomacrocyclic motif nor interpenetration.

AB - Structural and chemical influences on interpenetration have been investigated through the preparation and structural analysis of a series of seven chiral coordination polymers using a phenylalanine-substituted naphthalenediimide ligand (H2PheNDI). The reaction of H2PheNDI with MnII or CdII and a range of linear dipyridyl-based coligands forms a series of coordination polymers which vary greatly in terms of their topologies and interpenetration while largely retaining a common metallomacrocyclic motif. The metallomacrocyclic motif is found in a tube-like 1D coordination polymer poly-[Cd(bipy)(OH2)(PheNDI)] (2) and a closely related 2D polythreaded network poly-{[Cd2(bipy)2(PheNDI)2][Cd(bipy)(DMF)1.5(NO3)2(OH2)0.5]} (3) which are synthesized as pure phases under slightly different conditions. The longer 1,2-di(4-pyridyl)ethylene (dpe) ligand gives rise to a 2D coordination polymer poly-[Cd4(DMF)(dpe)4(OH2)2(PheNDI)4] (5) in which the metallomacrocycles are connected only "sideways" rather than as a tube. This difference allows for 2-fold 2D → 2D interpenetration, between two crystallographically distinct sheets, whereby the dpe passes through the metallomacrocycle, assisted by face-to-face aromatic interactions. The use of a larger dipyridyl ligand, N,N′-bis(4-pyridyl)naphthalenediimide (4pyNDI), yielded 3D coordination polymers with distorted pcu topologies of the form poly-[M2(PheNDI)2(4PyNDI)2] (M = Cd, 6; Mn, 7) which contain neither the metallomacrocyclic motif nor interpenetration.

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