We report the detection of fulvenallene (c-C5H4CCH2) in the direction of TMC-1 with the QUIJOTE1 line survey. Thirty rotational transitions with Ka = 0,1,2,3 and J = 9−15 were detected. The best rotational temperature fitting of the data is 9 K and a derived column density is (2.7 ± 0.3) × 1012 cm−2, which is only a factor of 4.4 below that of its potential precursor cyclopentadiene (c-C5H6), and 1.4–1.9 times higher than that of the ethynyl derivatives of cyclopentadiene. We searched for fulvene (c-C5H4CH2), a CH2 derivative of cyclopentadiene, for which we derive a 3σ upper limit to its column density of (3.5 ± 0.5) × 1012 cm−2. Upper limits were also obtained for toluene (C6H5CH3) and styrene (C6H5C2H3), the methyl and vinyl derivatives of benzene. Fulvenallene and ethynyl cyclopentadiene are likely formed in the reaction between cyclopentadiene (c-C5H6) and the ehtynyl radical (CCH). However, the bottom-up gas-phase synthesis of cycles in TMC-1 underestimates the abundance of cyclopentadiene by two orders of magnitude, which strengthens the need to study all possible chemical pathways to cyclisation in cold dark cloud environments, such as TMC-1. However, the inclusion of the reaction between C3H3+ and C2H4 produces a good agreement between model and observed abundances.

We report on the detection, for the first time in space, of the radical HCCCO and of pentacarbon monoxide, C5O. The derived column densities are (1.6 ± 0.2) × 1011 cm−2 and (1.5 ± 0.2) × 1010 cm−2, respectively. We have also analysed the data for all the molecular species of the families HCnO and CnO within our QUIJOTE’s line survey. Upper limits are obtained for HC4O, HC6O, C4O, and C6O. We report a robust detection of HC5O and HC7O based on 14 and 12 rotational lines detected with a signal-to-noise ratio ≥30 and ≥5, respectively. The derived N(HC3O)/N(HC5O) abundance ratio is 0.09 ± 0.03, while N(C3O)/N(C5O) is 80 ± 2, and N(HC5O)/N(HC7O) is 2.2 ± 0.3. As opposed to the cyanopolyyne family, HC2n + 1N, which shows a continuous decrease in the abundances with increasing n, the CnO and HCnO species show a clear abundance maximum for n = 3 and 5, respectively. They also show an odd and even abundance alternation, with odd values of n being the most abundant, which is reminiscent of the behaviour of CnH radicals, where in that case species with even values of n are more abundant. We explored the formation of these species through two mechanisms previously proposed, which are based on radiative associations between CnHm+ ions with CO and reactions of Cn̄ and CnH− anions with O atoms, and we found that several species, such as C5O, HC4O, and HC6O, are significantly overestimated. Our understanding of how these species are formed is incomplete as of yet. Other routes based on neutral-neutral reactions such as those of Cn and CnH carbon chains with O, OH, or HCO, could be behind the formation of these species.

We report on the discovery of the C 7 N − anion towards the starless core TMC-1 and towards the carbon-rich evolved star IRC +10216. We used the data of the QUIJOTE 1 line survey towards TMC-1 and found six lines in perfect harmonic frequency relation from J=27-26 up to J=32-31. The frequency of the lines can be reproduced with a rotational constant and a distortion constant of B=582.68490±0.00024 MHz and D=4.01±0.13 Hz, respectively. The standard deviation of the fit is 4 kHz. Towards IRC +10216, we identify 17 lines from J=27-26 up to J=43-42; their frequencies are also in harmonic relation, providing B=582.6827±0.00085 MHz and D=3.31±0.31 Hz. The nearly exact coincidence of the rotational and distortion constants in both sources points unambiguously to a common molecular carrier. Taking into account the chemical peculiarities of both sources, the carrier could be a radical or an anion. The radical can be discarded, as the observed lines belong to a singlet species. Hence, the most plausible carrier is an anion. High-level ab initio calculations indicate that C 7 N − , for which we compute a rotational constant of B=582.0 MHz and a dipole moment of 7.5 D, is the carrier of the lines in both sources. We predict the neutral C 7 N to have a ground electronic state 2 Π and a dipole moment of ∼1 D. Because of this low value of µ and to its much larger rotational partition function, its lines are expected to be well below the sensitivity of our data for both sources.

We report the detection in TMC-1 of the cation HCCS+ (X̃ 3Σ−), which is the protonated form of the widespread radical CCS. This is the first time that a protonated radical has been detected in a cold dark cloud. Twenty-six hyperfine components from twelve rotational transitions have been observed with the Yebes 40 m and IRAM 30m radio telescopes. We confidently assign the characteristic rotational spectrum pattern to HCCS+ based on the good agreement between the astronomical and theoretical spectroscopic parameters. The column density of HCCS+ is (1.1 ± 0.1)×1012 cm−2, and the CCS/HCCS+ abundance ratio is 50 ± 10, which is very similar to that of CS/HCS+ (35 ± 8) and CCCS/HCCCS+ (65 ± 20). From a state-of-the-art gas-phase chemical model, we conclude that HCCS+ is mostly formed by reactions of proton transfer from abundant cations such as HCO+, H3O+, and H3+ to the radical CCS.

We report the detection of the propargyl radical (CH2CCH) in the cold dark cloud TMC-1 in the λ 3 mm wavelength band. We recently discovered this species in space toward the same source at a wavelength of λ 8 mm. In those observations, various hyperfine components of the 20,2–10,1 rotational transition, at 37.5 GHz, were detected using the Yebes 40 m telescope. Here, we used the IRAM 30 m telescope to detect ten hyperfine components of the 50,5–40,4 rotational transition, lying at 93.6 GHz. The observed frequencies differ by 0.2 MHz with respect to the predictions from available laboratory data. This difference is significant for a radio-astronomical search for CH2CCH in interstellar sources with narrow lines. We thus included the measured frequencies in a new spectroscopic analysis to provide accurate frequency predictions for the interstellar search for propargyl at millimeter wavelengths. Moreover, we recommend that future searches for CH2CCH in cold interstellar clouds be carried out at λ 3 mm rather than at λ 8 mm. The 50,5–40,4 transition is about five times more intense than the 20,2–10,1 one in TMC-1, which implies that detecting the former requires about seven times less telescope time than detecting the latter. We constrain the rotational temperature of CH2CCH in TMC-1 to 9.9 ± 1.5 K, which indicates that the rotational levels of this species are thermalized at the gas kinetic temperature. The revised value of the column density of CH2CCH (including ortho and para species) is (1.0 ± 0.2) × 1014 cm−2, and thus the CH2CCH/CH3CCH abundance ratio is revised slightly higher, approaching one. This study opens the door to future detections of CH2CCH in other cold interstellar clouds, making it possible to further investigate the role of this very abundant hydrocarbon radical in the synthesis of large organic molecules, such as aromatic rings.