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Stereospecific generation of homochiral helices in coordination polymers built from enantiopure binaphthyl-based ligands

Stereospecific generation of homochiral helices in coordination polymers built from enantiopure binaphthyl-based ligands
Stereospecific generation of homochiral helices in coordination polymers built from enantiopure binaphthyl-based ligands
The novel enantiopure dipyridyl spacer 2,2?-dimethoxy-1,1?-binaphthyl-3,3?-bis(4-pyridyl-amido) (R)-L has been designed as a robust source of axial chirality to obtain helical coordination polymers. The reaction of (R)-L and the differently substituted dithiophosphato complexes [Ni((RO)2PS2)2] [R = Me (1), Et (2)] efficiently yielded coordination polymers (1·L)? and (2·L)?, respectively, consisting of helical chains in which the nickel(II) ions of the [Ni((RO)2PS2)2] units are bridged by the enantiopure L ligands. The obtained polymers differ in terms of the configuration at the metal centres, which is trans and cis for (1·L)? and (2·L)?, respectively. The cis configuration in (2·L)? generates a further element of chirality around the metal center, which occurs stereospecifically, as only one enantiomeric form is present, with homochiral helices packed with opposite screw sense in the crystal. The electronic and structural features of L, (1·L)?, and (2·L)? have been investigated by means of DFT theoretical calculations, and the theoretical results have been compared with the experimental ones coming from single-crystal X-ray diffraction. The cis/trans isomerism displayed by the metal centers in (1·L)? and (2·L)? has been tentatively explained on the basis of the results of theoretical calculations performed on hypothetical pentacoordinated intermediates.
1466-8033
8582-8590
Crespo Alonso, M.
fe2b30dd-f27a-4bfb-b03d-43c194a5c1c9
Arca, M.
d852c450-c522-47cb-a577-9babf59dd503
Isaia, F.
01929115-e3d5-4af1-b79b-439cfa32fd27
Lai, R.
98fa4fc8-3297-454b-9a82-6b62ae0923ce
Lippolis, V.
6890f6ab-6860-4752-9639-5bdfeef0e90d
Callear, S. K.
4ddca556-0ef8-461f-bb30-34c26531fd7b
Caricato, M.
46d02758-fa3f-4b88-9887-b085e9610c20
Pasini, D.
bff60c8a-faae-4c51-b494-6647e4310036
Coles, S. J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Aragoni, M. C.
5cbce4b0-4207-47f4-a6f3-4a2cc9ec9451
Crespo Alonso, M.
fe2b30dd-f27a-4bfb-b03d-43c194a5c1c9
Arca, M.
d852c450-c522-47cb-a577-9babf59dd503
Isaia, F.
01929115-e3d5-4af1-b79b-439cfa32fd27
Lai, R.
98fa4fc8-3297-454b-9a82-6b62ae0923ce
Lippolis, V.
6890f6ab-6860-4752-9639-5bdfeef0e90d
Callear, S. K.
4ddca556-0ef8-461f-bb30-34c26531fd7b
Caricato, M.
46d02758-fa3f-4b88-9887-b085e9610c20
Pasini, D.
bff60c8a-faae-4c51-b494-6647e4310036
Coles, S. J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Aragoni, M. C.
5cbce4b0-4207-47f4-a6f3-4a2cc9ec9451

Crespo Alonso, M., Arca, M., Isaia, F., Lai, R., Lippolis, V., Callear, S. K., Caricato, M., Pasini, D., Coles, S. J. and Aragoni, M. C. (2014) Stereospecific generation of homochiral helices in coordination polymers built from enantiopure binaphthyl-based ligands. CrystEngComm, 16 (36), 8582-8590. (doi:10.1039/C4CE01101E).

Record type: Article

Abstract

The novel enantiopure dipyridyl spacer 2,2?-dimethoxy-1,1?-binaphthyl-3,3?-bis(4-pyridyl-amido) (R)-L has been designed as a robust source of axial chirality to obtain helical coordination polymers. The reaction of (R)-L and the differently substituted dithiophosphato complexes [Ni((RO)2PS2)2] [R = Me (1), Et (2)] efficiently yielded coordination polymers (1·L)? and (2·L)?, respectively, consisting of helical chains in which the nickel(II) ions of the [Ni((RO)2PS2)2] units are bridged by the enantiopure L ligands. The obtained polymers differ in terms of the configuration at the metal centres, which is trans and cis for (1·L)? and (2·L)?, respectively. The cis configuration in (2·L)? generates a further element of chirality around the metal center, which occurs stereospecifically, as only one enantiomeric form is present, with homochiral helices packed with opposite screw sense in the crystal. The electronic and structural features of L, (1·L)?, and (2·L)? have been investigated by means of DFT theoretical calculations, and the theoretical results have been compared with the experimental ones coming from single-crystal X-ray diffraction. The cis/trans isomerism displayed by the metal centers in (1·L)? and (2·L)? has been tentatively explained on the basis of the results of theoretical calculations performed on hypothetical pentacoordinated intermediates.

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Published date: 28 September 2014
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 369305
URI: http://eprints.soton.ac.uk/id/eprint/369305
ISSN: 1466-8033
PURE UUID: 7ef309d6-5cbc-4a85-9057-85cecf0fadde
ORCID for S. J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 30 Sep 2014 14:07
Last modified: 18 Feb 2021 16:53

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Contributors

Author: M. Crespo Alonso
Author: M. Arca
Author: F. Isaia
Author: R. Lai
Author: V. Lippolis
Author: S. K. Callear
Author: M. Caricato
Author: D. Pasini
Author: S. J. Coles ORCID iD
Author: M. C. Aragoni

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