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A guest-responsive fluorescent 3D microporous metal-organic framework derived from a long-lifetime pyrene core

A guest-responsive fluorescent 3D microporous metal-organic framework derived from a long-lifetime pyrene core
A guest-responsive fluorescent 3D microporous metal-organic framework derived from a long-lifetime pyrene core
The carboxylate ligand 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy)—based on the strongly fluorescent long-lifetime pyrene core—affords a permanently microporous fluorescent metal-organic framework, [In2(OH)2(TBAPy)]·(guests) (1), displaying 54% total accessible volume and excellent thermal stability. Fluorescence studies reveal that both 1 and TBAPy display strong emission bands at 471 and 529 nm, respectively, upon excitation at 390 nm, with framework coordination of the TBAPy ligands significantly increasing the emission lifetime from 0.089 to 0.110 ms. Upon desolvation, the emission band for the framework is shifted to lower energy: however, upon re-exposure to DMF the as-made material is regenerated with reversible fluorescence behavior. Together with the lifetime, the emission intensity is strongly enhanced by spatial separation of the optically active ligand molecules within the MOF structure and is found to be dependent on the amount and chemical nature of the guest species in the pores. The quantum yield of the material is found to be 6.7% and, coupled with the fluorescence lifetime on the millisecond time scale, begins to approach the values observed for Eu(III)-cryptate-derived commercial sensors.
0002-7863
4119-4130
Stylianou, Kyriakos C.
0536c485-b0e9-4135-9f47-506bf5d51c1b
Heck, Romain
7b52a796-a105-4bac-b62d-b3e60978c9d4
Chong, Samantha Y.
2e23eea0-c8eb-48bb-8e69-7f3a50d0e812
Bacsa, John
8877bf1f-d692-4526-b61e-ee3f3c053204
Jones, James T.A.
bda2c4c2-7673-4efd-8a88-02d036f2b8db
Khimyak, Yaroslav Z.
7705dc0f-42a7-4a0b-aa57-f95ff886454d
Bradshaw, Darren
7677b11e-1961-447e-b9ba-4847a74bd4dd
Rosseinsky, Matthew J.
5590acd2-8dc9-4006-bbab-f3fa623c45ae
Stylianou, Kyriakos C.
0536c485-b0e9-4135-9f47-506bf5d51c1b
Heck, Romain
7b52a796-a105-4bac-b62d-b3e60978c9d4
Chong, Samantha Y.
2e23eea0-c8eb-48bb-8e69-7f3a50d0e812
Bacsa, John
8877bf1f-d692-4526-b61e-ee3f3c053204
Jones, James T.A.
bda2c4c2-7673-4efd-8a88-02d036f2b8db
Khimyak, Yaroslav Z.
7705dc0f-42a7-4a0b-aa57-f95ff886454d
Bradshaw, Darren
7677b11e-1961-447e-b9ba-4847a74bd4dd
Rosseinsky, Matthew J.
5590acd2-8dc9-4006-bbab-f3fa623c45ae

Stylianou, Kyriakos C., Heck, Romain, Chong, Samantha Y., Bacsa, John, Jones, James T.A., Khimyak, Yaroslav Z., Bradshaw, Darren and Rosseinsky, Matthew J. (2010) A guest-responsive fluorescent 3D microporous metal-organic framework derived from a long-lifetime pyrene core. Journal of the American Chemical Society, 132 (12), 4119-4130. (doi:10.1021/ja906041f). (PMID:20201518)

Record type: Article

Abstract

The carboxylate ligand 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy)—based on the strongly fluorescent long-lifetime pyrene core—affords a permanently microporous fluorescent metal-organic framework, [In2(OH)2(TBAPy)]·(guests) (1), displaying 54% total accessible volume and excellent thermal stability. Fluorescence studies reveal that both 1 and TBAPy display strong emission bands at 471 and 529 nm, respectively, upon excitation at 390 nm, with framework coordination of the TBAPy ligands significantly increasing the emission lifetime from 0.089 to 0.110 ms. Upon desolvation, the emission band for the framework is shifted to lower energy: however, upon re-exposure to DMF the as-made material is regenerated with reversible fluorescence behavior. Together with the lifetime, the emission intensity is strongly enhanced by spatial separation of the optically active ligand molecules within the MOF structure and is found to be dependent on the amount and chemical nature of the guest species in the pores. The quantum yield of the material is found to be 6.7% and, coupled with the fluorescence lifetime on the millisecond time scale, begins to approach the values observed for Eu(III)-cryptate-derived commercial sensors.

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e-pub ahead of print date: 4 March 2010
Published date: 31 March 2010
Organisations: Chemistry

Identifiers

Local EPrints ID: 340215
URI: http://eprints.soton.ac.uk/id/eprint/340215
ISSN: 0002-7863
PURE UUID: 8dda49fc-be92-4ba2-9fca-2f29276554c3
ORCID for Darren Bradshaw: ORCID iD orcid.org/0000-0001-5258-6224

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Date deposited: 15 Jun 2012 11:24
Last modified: 17 Dec 2019 01:39

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Contributors

Author: Kyriakos C. Stylianou
Author: Romain Heck
Author: Samantha Y. Chong
Author: John Bacsa
Author: James T.A. Jones
Author: Yaroslav Z. Khimyak
Author: Darren Bradshaw ORCID iD
Author: Matthew J. Rosseinsky

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