New York University Abu Dhabi, P.O. Box 129188, Abu Dhabi, UAE.
Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Hyogo, 679-5198, Japan.
Nat Commun. 2019 Mar 1;10(1):997. doi: 10.1038/s41467-019-08816-8.
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 E mol]. 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.
化学发光是一种能量传递过程,将基态反应物化学键中储存的能量通过高能激发中间体转化为光,这在溶液中是已知的,但在宏观晶态固体中仍然未被检测到。通过检测有机过氧化物厘米大小晶体的热诱导化学发光,我们在这里证明了通过体相晶体的热化学发光将热直接转化为光。加热洛芬过氧化物晶体至约 115°C 会导致可检测的蓝绿光发射,最大发射波长为 530nm,化学发光量子产率低 [(2.1±0.1)×10^-3]mol。固态和溶液中热化学发光的光谱比较表明,洛芬过氧化物的固态热化学发光是由于去质子化的洛芬发出的光。我们还选择了 1,2-二氧杂环乙烷、内过氧化物和酰基过氧化物,证明了热化学发光是晶体过氧化物的共同特性,发射光的颜色从蓝色到绿色到红色变化。