Singlet-triplet interconversion of diphenylmethylene. Energetics, dynamics and reactivities of different spin states

K. B. Eisenthal; N. J. Turro; E. V. Sitzmann; I. R. Gould; G. Hefferon; J. Langan; Y. Cha

doi:10.1016/S0040-4020(01)96394-X

Singlet-triplet interconversion of diphenylmethylene. Energetics, dynamics and reactivities of different spin states

K. B. Eisenthal, N. J. Turro, E. V. Sitzmann, I. R. Gould, G. Hefferon, J. Langan, Y. Cha

Research output: Contribution to journal › Article › peer-review

88 Scopus citations

Abstract

A combination of picosecond and nanosecond laser spectroscopy measurements, chemical quenching experiments and triplet sensitization experiments has allowed the determination of the rapid singlet to triplet and slower triplet to singlet intersystem crossing rates for diphenylmethylene in fluid solution at room temperature. It is shown that under the conditions of the kinetic measurements, singlet and triplet diphenylmethylene (¹DPM and ³DPM, respectively) are in rapid equilibrium relative to reactions, so that knowledge of the values of k_ST and k_TS allows determination of the equilibrium constant and change in free energy for the ¹DPM 〈 ³DPM process. The absolute reactivity of ¹DPM toward a series of alcohols has been determined and is discussed in terms of other current investigations of carbene reactivity.

Original language	English (US)
Pages (from-to)	1543-1554
Number of pages	12
Journal	Tetrahedron
Volume	41
Issue number	8
DOIs	https://doi.org/10.1016/S0040-4020(01)96394-X
State	Published - 1985
Externally published	Yes

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

Access to Document

10.1016/S0040-4020(01)96394-X

Cite this

@article{e823bbbb2cd44e30bae5e3887e263d75,

title = "Singlet-triplet interconversion of diphenylmethylene. Energetics, dynamics and reactivities of different spin states",

abstract = "A combination of picosecond and nanosecond laser spectroscopy measurements, chemical quenching experiments and triplet sensitization experiments has allowed the determination of the rapid singlet to triplet and slower triplet to singlet intersystem crossing rates for diphenylmethylene in fluid solution at room temperature. It is shown that under the conditions of the kinetic measurements, singlet and triplet diphenylmethylene (1DPM and 3DPM, respectively) are in rapid equilibrium relative to reactions, so that knowledge of the values of kST and kTS allows determination of the equilibrium constant and change in free energy for the 1DPM 〈 3DPM process. The absolute reactivity of 1DPM toward a series of alcohols has been determined and is discussed in terms of other current investigations of carbene reactivity.",

author = "Eisenthal, {K. B.} and Turro, {N. J.} and Sitzmann, {E. V.} and Gould, {I. R.} and G. Hefferon and J. Langan and Y. Cha",

note = "Funding Information: Acknowledgements-The authors thank the National Science Foundation. the Air Force Office of Scientific Research. and the Joint Services Electronics Program (DAAG-79-C-0079) for their generous support of this &&arch. The authors thank D. Griller, A. S. Nazran and J. C. Scaiano for sendinn us a preprint of their recent work on the react& of diphenylcarbene with methanol. The authors are most grateful to J. J. Zupanic, P. B. Grasse, S. C. Lapin and G. B. Schuster for communicating their results on fluorenylidene to us.",

year = "1985",

doi = "10.1016/S0040-4020(01)96394-X",

language = "English (US)",

volume = "41",

pages = "1543--1554",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Limited",

number = "8",

}

TY - JOUR

T1 - Singlet-triplet interconversion of diphenylmethylene. Energetics, dynamics and reactivities of different spin states

AU - Eisenthal, K. B.

AU - Turro, N. J.

AU - Sitzmann, E. V.

AU - Gould, I. R.

AU - Hefferon, G.

AU - Langan, J.

AU - Cha, Y.

N1 - Funding Information: Acknowledgements-The authors thank the National Science Foundation. the Air Force Office of Scientific Research. and the Joint Services Electronics Program (DAAG-79-C-0079) for their generous support of this &&arch. The authors thank D. Griller, A. S. Nazran and J. C. Scaiano for sendinn us a preprint of their recent work on the react& of diphenylcarbene with methanol. The authors are most grateful to J. J. Zupanic, P. B. Grasse, S. C. Lapin and G. B. Schuster for communicating their results on fluorenylidene to us.

PY - 1985

Y1 - 1985

N2 - A combination of picosecond and nanosecond laser spectroscopy measurements, chemical quenching experiments and triplet sensitization experiments has allowed the determination of the rapid singlet to triplet and slower triplet to singlet intersystem crossing rates for diphenylmethylene in fluid solution at room temperature. It is shown that under the conditions of the kinetic measurements, singlet and triplet diphenylmethylene (1DPM and 3DPM, respectively) are in rapid equilibrium relative to reactions, so that knowledge of the values of kST and kTS allows determination of the equilibrium constant and change in free energy for the 1DPM 〈 3DPM process. The absolute reactivity of 1DPM toward a series of alcohols has been determined and is discussed in terms of other current investigations of carbene reactivity.

AB - A combination of picosecond and nanosecond laser spectroscopy measurements, chemical quenching experiments and triplet sensitization experiments has allowed the determination of the rapid singlet to triplet and slower triplet to singlet intersystem crossing rates for diphenylmethylene in fluid solution at room temperature. It is shown that under the conditions of the kinetic measurements, singlet and triplet diphenylmethylene (1DPM and 3DPM, respectively) are in rapid equilibrium relative to reactions, so that knowledge of the values of kST and kTS allows determination of the equilibrium constant and change in free energy for the 1DPM 〈 3DPM process. The absolute reactivity of 1DPM toward a series of alcohols has been determined and is discussed in terms of other current investigations of carbene reactivity.

UR - http://www.scopus.com/inward/record.url?scp=0001433908&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001433908&partnerID=8YFLogxK

U2 - 10.1016/S0040-4020(01)96394-X

DO - 10.1016/S0040-4020(01)96394-X

M3 - Article

AN - SCOPUS:0001433908

SN - 0040-4020

VL - 41

SP - 1543

EP - 1554

JO - Tetrahedron

JF - Tetrahedron

IS - 8

ER -

Singlet-triplet interconversion of diphenylmethylene. Energetics, dynamics and reactivities of different spin states

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this