High quantum yield molecular bromine photoelimination from mononuclear platinum(IV) complexes

Alice Raphael Karikachery; Han Baek Lee; Mehdi Masjedi; Andreas Ross; Morgan A. Moody; Xiaochen Cai; Megan Chui; Carl D. Hoff; Paul R. Sharp

doi:10.1021/ic4004998

High quantum yield molecular bromine photoelimination from mononuclear platinum(IV) complexes

Alice Raphael Karikachery, Han Baek Lee, Mehdi Masjedi, Andreas Ross, Morgan A. Moody, Xiaochen Cai, Megan Chui, Carl D. Hoff, Paul R. Sharp

Chemistry

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30 Scopus citations

Abstract

Pt(IV) complexes trans-Pt(PEt₃)₂(R)(Br)₃ (R = Br, aryl and polycyclic aromatic fragments) photoeliminate molecular bromine with quantum yields as high as 82%. Photoelimination occurs both in the solid state and in solution. Calorimetry measurements and DFT calculations (PMe₃ analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br₂. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.

Original language	English (US)
Pages (from-to)	4113-4119
Number of pages	7
Journal	Inorganic Chemistry
Volume	52
Issue number	7
DOIs	https://doi.org/10.1021/ic4004998
State	Published - Apr 1 2013

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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High quantum yield molecular bromine photoelimination from mononuclear platinum(IV) complexes. / Raphael Karikachery, Alice; Lee, Han Baek; Masjedi, Mehdi; Ross, Andreas; Moody, Morgan A.; Cai, Xiaochen; Chui, Megan; Hoff, Carl D.; Sharp, Paul R.

In: Inorganic Chemistry, Vol. 52, No. 7, 01.04.2013, p. 4113-4119.

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

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abstract = "Pt(IV) complexes trans-Pt(PEt3)2(R)(Br)3 (R = Br, aryl and polycyclic aromatic fragments) photoeliminate molecular bromine with quantum yields as high as 82%. Photoelimination occurs both in the solid state and in solution. Calorimetry measurements and DFT calculations (PMe3 analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br2. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.",

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AU - Raphael Karikachery, Alice

AU - Lee, Han Baek

AU - Masjedi, Mehdi

AU - Ross, Andreas

AU - Moody, Morgan A.

AU - Cai, Xiaochen

AU - Chui, Megan

AU - Hoff, Carl D.

AU - Sharp, Paul R.

PY - 2013/4/1

Y1 - 2013/4/1

N2 - Pt(IV) complexes trans-Pt(PEt3)2(R)(Br)3 (R = Br, aryl and polycyclic aromatic fragments) photoeliminate molecular bromine with quantum yields as high as 82%. Photoelimination occurs both in the solid state and in solution. Calorimetry measurements and DFT calculations (PMe3 analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br2. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.

AB - Pt(IV) complexes trans-Pt(PEt3)2(R)(Br)3 (R = Br, aryl and polycyclic aromatic fragments) photoeliminate molecular bromine with quantum yields as high as 82%. Photoelimination occurs both in the solid state and in solution. Calorimetry measurements and DFT calculations (PMe3 analogs) indicate endothermic and endergonic photoeliminations with free energies from 2 to 22 kcal/mol of Br2. Solution trapping experiments with high concentrations of 2,3-dimethyl-2-butene suggest a radical-like excited state precursor to bromine elimination.

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High quantum yield molecular bromine photoelimination from mononuclear platinum(IV) complexes

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