Synthesis and characterization of lead metallated non-peripherally substituted octa-octyl tetrabenzo(aza)porphyrins showing face-to-face columnar stacking in the crystal phase
Synthesis and characterization of lead metallated non-peripherally substituted octa-octyl tetrabenzo(aza)porphyrins showing face-to-face columnar stacking in the crystal phase
The full range of porphyrin-phthalocyanine hybrids can be synthesized by treatment of 1,4-dioctylphthalonitrile with varying equivalents of MeMgBr to produce mixtures favoring specific hybrid structures and the tetrabenzoporphyrin in the extreme case. The individual macrocycles can be isolated in pure form as their magnesium derivatives and subsequently demetallated to give the parent metal-free compounds. Insertion of lead proceeded smoothly with all hybrids using lead (II) acetate. In the case of monoaza- and triaza-hybrids, the resulting materials could be recrystallized to give crystals suitable for X-ray diffraction. The crystal structures are distinctive from previously reported examples of non-peripherally substituted octaalkyl phthalocyanines and hybrids (metal-free and metallated, including with lead) and they each present infinite stacks of cofacial macrocycles linked through bridging lead ions which, as expected, lie outside of the macrocycle plane.
Lead phthalocyanines, columnar stacks, crystal structure, phthalocyanine-porphyrin hybrids, lead phthalocyanines
1285-1291
Vargas, Lydia Sosa
c6b5629a-01cd-40e4-b4ec-e487608d626f
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Chambrier, Isabelle
d3ad81b8-12d1-4f7a-bc04-99da7f4c0d50
Cook, Michael J.
9b30e5b0-b828-46a7-a1f6-cd758c3c6c74
Cammidge, Andrew N.
e7a6b5be-5613-416e-8f1a-40b4744ecf65
1 October 2023
Vargas, Lydia Sosa
c6b5629a-01cd-40e4-b4ec-e487608d626f
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Chambrier, Isabelle
d3ad81b8-12d1-4f7a-bc04-99da7f4c0d50
Cook, Michael J.
9b30e5b0-b828-46a7-a1f6-cd758c3c6c74
Cammidge, Andrew N.
e7a6b5be-5613-416e-8f1a-40b4744ecf65
Vargas, Lydia Sosa, Coles, Simon J., Tizzard, Graham J., Chambrier, Isabelle, Cook, Michael J. and Cammidge, Andrew N.
(2023)
Synthesis and characterization of lead metallated non-peripherally substituted octa-octyl tetrabenzo(aza)porphyrins showing face-to-face columnar stacking in the crystal phase.
Journal of Porphyrins and Phthalocyanines, 27 (7-10), .
(doi:10.1142/S1088424623500876).
Abstract
The full range of porphyrin-phthalocyanine hybrids can be synthesized by treatment of 1,4-dioctylphthalonitrile with varying equivalents of MeMgBr to produce mixtures favoring specific hybrid structures and the tetrabenzoporphyrin in the extreme case. The individual macrocycles can be isolated in pure form as their magnesium derivatives and subsequently demetallated to give the parent metal-free compounds. Insertion of lead proceeded smoothly with all hybrids using lead (II) acetate. In the case of monoaza- and triaza-hybrids, the resulting materials could be recrystallized to give crystals suitable for X-ray diffraction. The crystal structures are distinctive from previously reported examples of non-peripherally substituted octaalkyl phthalocyanines and hybrids (metal-free and metallated, including with lead) and they each present infinite stacks of cofacial macrocycles linked through bridging lead ions which, as expected, lie outside of the macrocycle plane.
Text
Cammidge2305
- Accepted Manuscript
More information
Accepted/In Press date: 21 March 2023
e-pub ahead of print date: 14 June 2023
Published date: 1 October 2023
Additional Information:
Acknowledgments: We thank CONACYT, Mexico, and UEA for funding (LXS-V). MJC gratefully thanks the Leverhulme Foundation for the award of a Leverhulme Emeritus Fellow- ship. SJC and GJT thank the EPSRC for funding.
Keywords:
Lead phthalocyanines, columnar stacks, crystal structure, phthalocyanine-porphyrin hybrids, lead phthalocyanines
Identifiers
Local EPrints ID: 481071
URI: http://eprints.soton.ac.uk/id/eprint/481071
ISSN: 1088-4246
PURE UUID: 7325a3ae-33c9-42e7-97b7-bfd7b61d20ce
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Date deposited: 15 Aug 2023 16:44
Last modified: 06 Jun 2024 01:40
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Contributors
Author:
Lydia Sosa Vargas
Author:
Isabelle Chambrier
Author:
Michael J. Cook
Author:
Andrew N. Cammidge
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