PP bond photophysics in an Ar-PP-Ar diphosphene

Huo Lei Peng, John L. Payton, John D. Protasiewicz, M. Cather Simpson

Research output: Contribution to journalArticle

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Abstract

The details of the photophysics of a diphosphene DmpPPDmp (Dmp: 2,6-Mes 2C 6H 3) have been examined experimentally and computationally. Femtosecond transient absorption spectroscopy has been used to probe the dynamics of the S 1 and S 2 excited states of DmpPPDmp, through excitation at 480 and 400 nm, respectively. The molecule returns to S 0 on sub-nanosecond timescales; no irreversible photochemistry is observed. The S 2 state is observed in the transient spectra with an absorption feature at the red end of the visible spectrum. Its lifetime was measured to be 275 fs. The S 1 state does not absorb appreciably in the probe wavelength range. Excitation into either of these states leads to transient absorption signals in the 400-600 nm region that exhibit a rise time longer than the measured instrument response function, indicating that they do not arise from the initially excited state. These bands decay biexponentially, with lifetimes of ∼20 ps and of a few hundred ps. Calculations at the CASSCF(8,6)/6-31G** and CASPT2(8,6)/6- 31G**//CASSCF(8,6)/6-31G** levels support these assignments, and underpin an initial working model that involves participation of phenyl torsional twisting motions and the possibility of rapid intersystem crossing to the low-lying triplet manifold.

Original languageEnglish (US)
Pages (from-to)13204-13209
Number of pages6
JournalDalton Transactions
Volume41
Issue number42
DOIs
StatePublished - Nov 14 2012

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Excited states
Photochemical reactions
Absorption spectroscopy
Wavelength
Molecules

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Peng, H. L., Payton, J. L., Protasiewicz, J. D., & Simpson, M. C. (2012). PP bond photophysics in an Ar-PP-Ar diphosphene. Dalton Transactions, 41(42), 13204-13209. https://doi.org/10.1039/c2dt30568b

PP bond photophysics in an Ar-PP-Ar diphosphene. / Peng, Huo Lei; Payton, John L.; Protasiewicz, John D.; Simpson, M. Cather.

In: Dalton Transactions, Vol. 41, No. 42, 14.11.2012, p. 13204-13209.

Research output: Contribution to journalArticle

Peng, HL, Payton, JL, Protasiewicz, JD & Simpson, MC 2012, 'PP bond photophysics in an Ar-PP-Ar diphosphene', Dalton Transactions, vol. 41, no. 42, pp. 13204-13209. https://doi.org/10.1039/c2dt30568b
Peng HL, Payton JL, Protasiewicz JD, Simpson MC. PP bond photophysics in an Ar-PP-Ar diphosphene. Dalton Transactions. 2012 Nov 14;41(42):13204-13209. https://doi.org/10.1039/c2dt30568b
Peng, Huo Lei ; Payton, John L. ; Protasiewicz, John D. ; Simpson, M. Cather. / PP bond photophysics in an Ar-PP-Ar diphosphene. In: Dalton Transactions. 2012 ; Vol. 41, No. 42. pp. 13204-13209.
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