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Triplet Distribution in a Symmetrical Zinc(II) Porphyrin-BODIPY Pentameric Array

Lookup NU author(s): Dr Ozgur Bozdemir, Emeritus Professor Anthony Harriman


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© 2020 American Chemical Society.A symmetrical molecular array has been synthesized comprising a central zinc(II) 5,10,15,20-tetraphenylporphyrin with identical boron dipyrromethene (BODIPY) units appended at each of the meso sites. Excitation of any subunit causes a cascade of electronic energy-transfer steps, ultimately leading to the BODIPY triplet-excited state in high yield. Coincidentally, the triplet energy levels of the zinc(II) porphyrin and BODIPY appendage are closely balanced such that an equilibrium is established at both 77 K and room temperature. This fast equilibration allows global distribution of the triplet exciton around the array, leading to a significantly increased capture volume for bimolecular quenching and a substantial increase in the rate constant for bimolecular triplet-triplet annihilation. The corresponding free-base porphyrin analogue does not favor triplet exciton decentralization because of the large disparity in the electronic energy levels.

Publication metadata

Author(s): Bozdemir OA, Gultekin DD, Harriman A

Publication type: Article

Publication status: Published

Journal: Journal of Physical Chemistry A

Year: 2020

Volume: 124

Issue: 51

Pages: 10736–10747

Print publication date: 24/12/2020

Online publication date: 09/12/2020

Acceptance date: 02/04/2016

ISSN (print): 1089-5639

ISSN (electronic): 1520-5215

Publisher: American Chemical Society


DOI: 10.1021/acs.jpca.0c09243


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