Photophysics of Soret-Excited Tin(IV) Porphyrins in Solution

The photophysics of low-chlorin tin(IV) tetraphenylporphyrin dihydroxide, a core building block for axially substituted supramolecular tin porphyrin constructs, has been studied in a variety of hydrogen-bonding, nonpolar, and aprotic polar solvents using steady-state, nanosecond, and femtosecond tim...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-08, Vol.117 (33), p.7833-7840
Main Authors: Ghiggino, Kenneth P, Giri, Neeraj Kumar, Hanrieder, Jordan, Martell, Jonathon D, Müller, Jens, Paige, Matthew F, Robotham, Benjamin, Szmytkowski, Jędrzej, Steer, Ronald P
Format: Article
Language:English
Subjects:
Atomic and molecular physics
Continuous operation
Exact sciences and technology
Femtosecond
Fluorescence
Fluorescence and phosphorescence spectra
Fluorescence and phosphorescence
radiationless transitions, quenching (intersystem crossing, internal conversion)
Frequency conversion
harmonic generation, including high-order harmonic generation
Fundamental areas of phenomenology (including applications)
Laser optical systems: design and operation
Metalloporphyrins - chemistry
Molecular properties and interactions with photons
Molecular Structure
Monomers
Nanostructure
Nonlinear optics
Optics
Photochemical Processes
Photons
Physics
Porphyrins
Solutions
Solvents
Spectrophotometry, Ultraviolet
Tin - chemistry
Upconversion
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Summary:The photophysics of low-chlorin tin(IV) tetraphenylporphyrin dihydroxide, a core building block for axially substituted supramolecular tin porphyrin constructs, has been studied in a variety of hydrogen-bonding, nonpolar, and aprotic polar solvents using steady-state, nanosecond, and femtosecond time-resolved emission, and femtosecond time-resolved absorption methods. In hydrogen-bonding solvents the metalloporphyrin exists as solvated monomers, and its Soret-excited S2 state in these solvents exhibits the expected linear energy gap law relationship with first-order population decay times in the 0.8 to 1.7 ps range. Evidence is presented that this metalloporphyrin aggregates in other solvents at the concentrations typically used for these ultrafast measurements and yields species-averaged time-resolved data. Cw laser excitation in the Q-band under deaerated conditions produces weak S2–S0 fluorescence (photon upconversion) as a result of triplet–triplet annihilation.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp406025j