dc.contributor.author | Nicolaïdes, Andrew N. | en |
dc.contributor.author | Enyo, T. | en |
dc.contributor.author | Miura, D. | en |
dc.contributor.author | Tomioka, H. | en |
dc.creator | Nicolaïdes, Andrew N. | en |
dc.creator | Enyo, T. | en |
dc.creator | Miura, D. | en |
dc.creator | Tomioka, H. | en |
dc.date.accessioned | 2019-11-21T06:21:42Z | |
dc.date.available | 2019-11-21T06:21:42Z | |
dc.date.issued | 2001 | |
dc.identifier.uri | http://gnosis.library.ucy.ac.cy/handle/7/55898 | |
dc.description.abstract | A series of para-conjugatively coupled phenylenecarbenonitrenes {(4-nitrenophenyl)methylene (3a), (4-nitrenophenyl)fluoromethylene (3b), (4-nitrenophenyl)chloromethylene (3c), and (4-nitrenophenyl)bromomethylene (3d)} were generated in argon matrix at low temperature (10 or 13 K) and characterized by IR and UV/vis spectroscopy. Density functional theory (B3LYP/6-31G(d)) and ab initio (MCSCF, CASPT2) methods were used to study the ground- and some low-lying excited states of 3a-d. The experimental and computational data suggest that 3a-d have singlet ground states (S0) and can be thought of as quinonoidal biradicals. In all cases, the lowest triplet (T1) and quintet (Q1) states lie about 2 kcal mol-1 and 28-29 kcal mol-1, respectively, higher in energy than S0. On the other hand the substituent is found to have a significant effect on the relative energy of the second excited triplet (T2) state. This state tends to become relatively more stable as the ability of the substituent to enforce a closed-shell configuration at the carbene subunit increases. Interestingly, the energy difference between the T2 and S0 states in 3a-d is found to depend linearly on the S-T gap of the corresponding phenylcarbenes 7a-d. This relationship is helpful in predicting when a substituted p-phenylenecarbenonitrene may have a triplet ground state instead of a singlet one. | en |
dc.source | Journal of the American Chemical Society | en |
dc.source.uri | https://www.scopus.com/inward/record.uri?eid=2-s2.0-0034820005&doi=10.1021%2fja003709e&partnerID=40&md5=452d0a507736b18ba64b5db0069f6a0d | |
dc.subject | article | en |
dc.subject | unclassified drug | en |
dc.subject | chemical analysis | en |
dc.subject | density | en |
dc.subject | energy | en |
dc.subject | low temperature | en |
dc.subject | molecular interaction | en |
dc.subject | Low temperature effects | en |
dc.subject | infrared spectroscopy | en |
dc.subject | ultraviolet spectroscopy | en |
dc.subject | Argon | en |
dc.subject | conformation | en |
dc.subject | carbenoid | en |
dc.subject | Halogen compounds | en |
dc.subject | carbene | en |
dc.subject | halogen | en |
dc.subject | Electron energy levels | en |
dc.subject | 4 phenylenecarbenonitrine | en |
dc.subject | Biradicals | en |
dc.subject | nuclear magnetic resonance | en |
dc.title | p-phenylenecarbenonitrene and its halogen derivatives: How does resonance interaction between a nitrene and a carbene center affect the overall electronic configuration? | en |
dc.type | info:eu-repo/semantics/article | |
dc.identifier.doi | 10.1021/ja003709e | |
dc.description.volume | 123 | |
dc.description.issue | 11 | |
dc.description.startingpage | 2628 | |
dc.description.endingpage | 2636 | |
dc.author.faculty | 002 Σχολή Θετικών και Εφαρμοσμένων Επιστημών / Faculty of Pure and Applied Sciences | |
dc.author.department | Τμήμα Χημείας / Department of Chemistry | |
dc.type.uhtype | Article | en |
dc.description.notes | <p>Cited By :28</p> | en |
dc.source.abbreviation | J.Am.Chem.Soc. | en |