Thermodynamic and Spectroscopic Scales of Halogen‐Bond Basicity and Affinity

doi:10.1002/9780470681909.ch5

Lewis Basicity and Affinity Scales 2009

DOI: 10.1002/9780470681909.ch5

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Thermodynamic and Spectroscopic Scales of Halogen‐Bond Basicity and Affinity

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2020

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Halogen Bonding Facilitates Intersystem Crossing in Iodo-BODIPY Chromophores

Lee

Malamakal

Chenoweth

et al. 2020

J. Phys. Chem. Lett.

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BODIPY chromophores can serve as organic-based triplet photosensitizers for a wide range of applications. To perform this function, the formation of the triplet state is critical, and a better understanding of how to modulate the formation of the triplet state could lead to further advances in BODIPY-based sensitizers for solar energy conversion and photodynamic therapy. In this work we investigate the ability of halogen bonding, a noncovalent solvent interaction, to facilitate intersystem crossing in a diiodo-BODIPY. Ultrafast transient absorption spectroscopy is applied to diiodo-BODIPY in the presence of pyridine-based halogen bonding solvent molecules to determine the rate constants for intersystem crossing. We find that halogen bonding facilitates the formation of the triplet state by increasing the intersystem crossing rate constant of diiodo-BODIPY. The results are interpreted in terms of the Marcus expression for intersystem crossing. Quantum chemical calculations show that halogen bonding acts to alter both the spin–orbit coupling terms and the relative energetics of the singlet and triplet states.

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Halogen Bonding Facilitates Intersystem Crossing in Iodo-BODIPY Chromophores

Lee

Malamakal

Chenoweth

et al. 2020

J. Phys. Chem. Lett.

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show abstract

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Thermodynamic and Spectroscopic Scales of Halogen‐Bond Basicity and Affinity

Cited by 1 publication

References 240 publications

Halogen Bonding Facilitates Intersystem Crossing in Iodo-BODIPY Chromophores

Halogen Bonding Facilitates Intersystem Crossing in Iodo-BODIPY Chromophores

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