A microporous metal–organic framework with open metal sites for selective sensing Fe3+,  CrO42- and nitrobenzene

Recently, the presence of fullerenes in the interstellar medium (ISM) has been confirmed and new findings suggest that these fullerenes may possibly form from polycyclic aromatic hydrocarbons (PAHs) in the ISM. Moreover, the first confirmed identification of two strong diffuse interstellar bands (DIBs) with the fullerene, C + 60 , connects the long standing suggestion that various fullerenes could be DIB carriers. These new discoveries justify reassessing the overall importance of interstellar fullerene compounds, including fullerenes of various sizes with endohedral or exohedral inclusions and heterofullerenes (EEHFs). The phenomenology of fullerene compounds is complex. In addition to fullerene formation in grain shattering, fullerene formation from fully dehydrogenated PAHs in diffuse interstellar clouds could perhaps transform a significant percentage of the tail of low-mass PAH distribution into fullerenes including EEHFs. But many uncertain processes make it extremely difficult to assess their expected abundance, composition and size distribution, except for the substantial abundance measured for C + 60 . EEHFs share many properties with pure fullerenes, such as C 60 , as regards stability, formation/destruction and chemical processes, as well as many basic spectral features. Because DIBs are ubiquitous in all lines of sight in the ISM, we address several questions about the interstellar importance of various EEHFs, especially as possible carriers of diffuse interstellar bands. Specifically, we discuss basic interstellar properties and the likely contributions of fullerenes of various sizes and their charged counterparts such as C + 60 , and then in turn: 1) metallofullerenes; 2) heterofullerenes; 3) fulleranes; 4) fullerene-PAH compounds; 5) H 2 @C 60 . From this reassessment of the literature and from combining it with known DIB line identifications, we conclude that the general landscape of interstellar fullerene compounds is probably much richer than heretofore realized. EEHFs, together with pure fullerenes of various sizes, have many properties necessary to be suitably carriers of DIBs: carbonaceous nature; stability and resilience in the harsh conditions of the ISM; existing with various heteroatoms and ionization states; relatively easy formation; few stable isomers; spectral lines in the right spectral range; various and complex energy internal conversion; rich Jahn-Teller fine structure. This is supported by the first identification of a DIB carrier as C + 60 . Unfortunately, the lack of any precise information about the complex optical spectra of EEHFs and most pure fullerenes other than C 60 and about their interstellar abundances still precludes definitive assessment of the importance of fullerene compounds as DIB carriers. Their compounds could significantly contribute to DIBs, but it still seems difficult that they are the only important DIB carriers. Regardless, DIBs appear as the most promising way of tracing the interstellar abundances of various fullerene compounds if the breakthr...

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“…This immediately shows (see e.g. Stener et al 2002), even if the transfer of two electrons dominates (Wang et al 1993).…”

Section: Basic Properties Of Endofullerenesmentioning

confidence: 99%

Interstellar fullerene compounds and diffuse interstellar bands

Omont

2016

A&A

100

103

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“…[26,29] In addition, the HOMO/LUMO energy were estimated by O3LYP, PBE, B3LYP, and TPSSh functionals with 6-311G* basis set. [39][40][41][42][43] All the stacking motifs of studied compounds from 2 to 9 are unknown. Considering the fact that the molecular structures of our studied compounds are similar, it is rational to assume that TPB and its derivatives have similar face to face molecular packing way between the adjacent molecules.…”

Section: Computational Detailsmentioning

confidence: 99%

Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

Hu¹,

Yin²,

Chaitanya³

et al. 2016

Croat. Chem. Acta

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Abstract:The electronic structures and charge transport properties of 1,3,5-tripyrrolebenzene (TPB) and its substituted derivatives with -F and -CN groups have been investigated by DFT calculations in combination with the Marcus hopping model. The dimer geometry was optimized by density functional theory method with dispersion force correction being included (DFT-D). Consequently, the charge transfer integral was evaluated. The calculation results show that the introduction of electron-withdrawing substituents does not significantly change the bond lengths and molecular symmetry of TPB, but lower the coplanarity between the pyrrole and benzene rings, especially in the case of CN substitution. Meanwhile, the introduction of electron-withdrawing groups can decrease the energy of the frontier molecular orbital and enhance the air stability. Fluorination makes the λe increase obviously while cyanation dose not. Generally speaking, the λe values of the title compounds are larger than their λh. Except for compounds 6 and 9, all others keep the face to face packing or have a slight slip in dimers, but the center of mass distances increase after fluorination or cyanation due to the distortion of the monomer's coplanarity. The predicted quasi-one-dimensional electron mobility of the dimers is up to 0.433 cm 2 ·V -1 ·s -1 at 298.15 K. The electron injection barriers of 2 and 7 are lower than that of TPB. The TPB derivatives of 1, 2, and 7 are potential n-channel materials with the high electron mobility.

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“…catalytic oxycarbonylation of methanol [1][2][3][4][5][6], via CO 2 insertion into epoxides [7] or by alcoholysis of urea [8], propelled the scientists interest in the exploitation of these compounds as safe analogues for phosgene, dimethyl sulfate and methyl halides [9].…”

Section: Introductionmentioning

confidence: 99%

5-Membered cyclic ethers via phenonium ion mediated cyclization through carbonate chemistry

Aricò

Maranzana

Musolino

et al. 2017

Pure and Applied Chemistry

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Cyclization of 2-(2-hydroxyethyl)phenol via DMC chemistry in acidic conditions is herein discussed for the first time. Reaction conditions have been investigated and optimized. This substrate is quite appealing as it incorporates a 2-hydroxyethyl moiety in ortho to the aromatic hydroxyl group capable of stabilizing the related phenonium ion. When the reaction mechanism was investigated via theoretical calculations, the results suggest that the most favorable pathway encompasses a DMC-mediated formation of the phenonium ion that is converted into the 2-(2-methoxyethyl)phenol. The related cyclic ether is then formed via intramolecular cyclization of this intermediate. This peculiar cyclization reaction is another example of the versatility of DMC herein used as solvent, methoxycarbonylation agent and leaving group in the intramolecular cyclization leading to the phenonium ion.

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A microporous metal–organic framework with open metal sites for selective sensing Fe3+, CrO42- and nitrobenzene

Cited by 35 publications

References 25 publications

Interstellar fullerene compounds and diffuse interstellar bands

Interstellar fullerene compounds and diffuse interstellar bands

Theoretical Investigation on Charge Transfer Properties of 1,3,5-Tripyrrolebenzene (TPB) and its Derivatives with Electron-withdrawing Substituents

5-Membered cyclic ethers via phenonium ion mediated cyclization through carbonate chemistry

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