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 - Funding Information:
This work was financially supported by New York University Abu Dhabi (NYUAD). The research was in part performed by using the Core Technology Platform resources at NYUAD. We thank Dr. Matthew O’Connor, Dr. Rachid Rezgui and Guowei He for the technical support. The computations were carried out on the High Performance Computing resources at NYUAD. The micro-focus IR experiments were performed at the SPring-8 synchrotron beamline BL43IR under proposal number 2018A1235.
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 -