Optical spectrum of the cyanoadamantane radical cation

Infrared spectrum of the 1-cyanoadamantane cation: evidence of hydrogen transfer and cage-opening upon ionization

“…33,39–41 However, EPD spectroscopy performed for Ada + and Dia + reveal broad and unresolved spectral bands spanning the whole visible frequency range, even when cooled to cryogenic temperatures below 20 K. 12,13,42 This spectral broadness is attributed to a combination of short excited state lifetimes (∼20 fs) and Franck–Condon congestion of closely lying vibrational modes resulting in rapid relaxation of the excited state. 12–14 Thus, these experiments exclude small bare diamondoid cations as possible carriers of the DIBs.…”

“…50 Its electronic EPD spectrum features similar spectral broadness to the bare diamondoid cations which, combined with the relative ease by which it fragments, thus discounts it as a viable DIB carrier. 14 This spectral broadness, in addition to the cage-opening mechanism observed for Ama + , motivates the investigation of the geometric structure of AdCN + via IR spectroscopy. Moreover, the most intense fragment peak observed at m / z 134 in the AdCN mass spectrum is attributed to the loss of neutral HCN.…”

“…1,2 These molecules were first discovered in crude oil extracts and are accumulating interest in multiple disciplines including molecular electronics, 3–5 nanotechnology, 6–8 medicinal chemistry, 9 chemical synthesis, 10,11 and astrochemistry due to their thermodynamic and chemical stability. 12–16 Lower diamondoids (those possessing only one structural isomer) are able to be synthesised in the laboratory and can be functionalized to obtain derivatives with properties that are tailored to specific applications. 3–5,17–22 One such example is amantadine (C 10 H 15 NH 2 , Ama) which is used to treat Parkinson's disease as well as being an antiviral agent.…”

“…In addition to biochemistry and pharmaceutical applications, diamondoids and their functionalized derivatives are being actively researched in the field of astrochemistry. 12–14,16,33–35 It has been hypothesized that diamondoids may account for over 5% of cosmic and 40% of tertiary carbon in interstellar environments. 15,16 Evidence suggesting their presence in the interstellar medium (ISM) first came from nanodiamond material discovered in extrasolar meteorites at concentrations up to 400 ppm.…”

“…Functionalized derivatives such as cationic diamondoid nitriles were proposed as more promising candidates because substituents modify the electronic structure and allow for new transitions to occur. 13,14 Organic and inorganic molecules possessing nitrile groups are also commonly observed in the interstellar environment by radio astronomy due to intense rotational transitions brought about by their large electric dipole moments. 43–46…”