TY - JOUR
T1 - Thermochemiluminescent Peroxide Crystals
AU - Schramm, Stefan
AU - Karothu, Durga Prasad
AU - Lui, Nathan M.
AU - Commins, Patrick
AU - Ahmed, Ejaz
AU - Catalano, Luca
AU - Li, Liang
AU - Weston, James
AU - Moriwaki, Taro
AU - Solntsev, Kyril M.
AU - Naumov, Pance
N1 - Publisher Copyright:
© 2019, The Author(s).
PY - 2019/3/1
Y1 - 2019/3/1
N2 - Chemiluminescence, a process of transduction of energy stored within chemical bonds of ground-state reactants into light via high-energy excited intermediates, is known in solution, but has remained undetected in macroscopic crystalline solids. By detecting thermally induced chemiluminescence from centimeter-size crystals of an organic peroxide here we demonstrate direct transduction of heat into light by thermochemiluminescence of bulk crystals. Heating of crystals of lophine hydroperoxide to ~115 °C results in detectable emission of blue-green light with maximum at 530 nm with low chemiluminescent quantum yield [(2.1 ± 0.1) × 10 ‒7 E mol ‒1 ]. Spectral comparison of the thermochemiluminescence in the solid state and in solution revealed that the solid-state thermochemiluminescence of lophine peroxide is due to emission from deprotonated lophine. With selected 1,2-dioxetane, endoperoxide and aroyl peroxide we also establish that the thermochemiluminescence is common for crystalline peroxides, with the color of the emitted light varying from blue to green to red.
AB - Chemiluminescence, a process of transduction of energy stored within chemical bonds of ground-state reactants into light via high-energy excited intermediates, is known in solution, but has remained undetected in macroscopic crystalline solids. By detecting thermally induced chemiluminescence from centimeter-size crystals of an organic peroxide here we demonstrate direct transduction of heat into light by thermochemiluminescence of bulk crystals. Heating of crystals of lophine hydroperoxide to ~115 °C results in detectable emission of blue-green light with maximum at 530 nm with low chemiluminescent quantum yield [(2.1 ± 0.1) × 10 ‒7 E mol ‒1 ]. Spectral comparison of the thermochemiluminescence in the solid state and in solution revealed that the solid-state thermochemiluminescence of lophine peroxide is due to emission from deprotonated lophine. With selected 1,2-dioxetane, endoperoxide and aroyl peroxide we also establish that the thermochemiluminescence is common for crystalline peroxides, with the color of the emitted light varying from blue to green to red.
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U2 - 10.1038/s41467-019-08816-8
DO - 10.1038/s41467-019-08816-8
M3 - Article
C2 - 30824701
AN - SCOPUS:85062263394
SN - 2041-1723
VL - 10
SP - 997
JO - Nature communications
JF - Nature communications
IS - 1
M1 - 997
ER -