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1.
Intermediate diradicals which occur in the Paterno–Büchi photocycloaddition and in the Norrish type I photoreactions have been calculated taking into account the spin–orbit coupling (SOC) between the singlet (S) and triplet (T) states. Reaction paths for the photocycloaddition of formaldehyde to ethene and the diradical products of the α-cleavage of cyclohexanone have been optimized by the MNDO CI method for a number of different singlet and triplet states. SOC integrals are calculated by an effective one-electron approximation. Intermediate diradicals in the Paterno–Büchi reaction and the SOC effects are also studied ab initio with CAS SCF geometry optimization in a TZV basis set. Both methods predict a large SOC matrix element between the S and T states in the course of the C–C attack, while the SOC integral is two orders of magnitude smaller for the diradical produced in the C–O attack. In the Norrish type I photoreaction the oxygen atom also produces some nonzero contribution to the SOC integral which governs intersystem crossing in a ·C–C· diradical. For the diradicals produced by the α-cleavage of cyclohexanone a vibronic interaction is responsible for the SOC mixing between the lowest S and T states. The importance of one-center versus two-center SOC contributions in diradicals is briefly discussed. 相似文献
2.
Prabuddha Bhattacharya Monisha Singha Eshani Das Arundhoti Mandal Manasi Maji Amit Basak 《Tetrahedron letters》2018,59(32):3033-3051
Garratt-Braverman cyclization has emerged as one of the simplest synthetic tool to construct two consecutive CC bonds leading to the formation of various important structural scaffolds having significance in the field of therapeutics and material science. The strategic design of suitable precursor for this cycloaromatization reaction involves the deep understanding of reaction pathways involving diradicals and ions. On the other hand, the reaction offers an unprecedented mechanistic paradox for the chemists to solve. This report aims at outlining the recent mechanistic and synthetic developments with special emphasis on the research outcomes from our laboratory. 相似文献
3.
Ziqi Zhu Di Zhang Tongtong Xiao Yu-Hui Fang Xiao Xiao Xiao-Ge Wang Prof. Shang-Da Jiang Prof. Dahui Zhao 《Angewandte Chemie (International ed. in English)》2023,62(49):e202314900
Stable carbon-based polyradicals exhibiting strong spin-spin coupling and slow depolarization processes are particularly attractive functional materials. A new molecular motif synthesized by a convenient method that allows the integration of stable, high-spin radicals to (hetero)aromatic polycycles has been developed, as illustrated by a non-Kekulé diradical showing a triplet ground state with long persistency (τ1/2≈31 h) in air. Compared to the widely used 1,3-phenylene, the newly designed (diaza)pyrene-4,10-diyl moiety is for the first time demonstrated to confer ferromagnetic (FM) spin coupling, allowing delocalized non-disjoint SOMOs. With the X-ray crystallography unambiguously proving the diradical structure, the triplet ground state was thoroughly characterized. A large ΔES-T of 1.1 kcal/mol, proving the strong FM coupling effect, was revealed consistently by superconducting quantum interference device (SQUID) measurements and variable-temperature electron paramagnetic resonance (EPR) spectroscopy, while the zero-field splitting and triplet nutation characters were examined by continuous-wave and pulsed EPR spectroscopy. A millisecond spin-lattice relaxation time was also detected. The current study not only offers a new molecular motif enabling FM coupling between carbon-based spins, but more importantly presents a general method for installing stable polyradicals into functional π-systems. 相似文献
4.
Barry K. Carpenter 《Angewandte Chemie (International ed. in English)》1998,37(24):3340-3350
An unexpected yes is the answer the author gives to the following questions: If a reactive intermediate was faced with two equally high energy barriers to product formation, could the kinetic product ratio ever be anything other than 1:1? If the two barriers were of unequal height, could there ever be a preference to form the product that corresponds to the higher barrier pathway? The basis for this yes are the results from molecular dynamics simulations and experiments that suggest that the interpretation of reaction mechanisms by statistical models is not always correct. 相似文献
5.
《中国化学》2018,36(6):487-490
Two‐electron oxidations of three 1,2‐di(bisphenylamino)‐benzenes afforded a class of nitrogen analogues of o‐quinodimethane. Their electronic structures in the ground state were studied by spectroscopic techniques including EPR and UV‐vis absorption spectroscopy. They have open‐shell singlet ground states with thermally accessible triplet states. One of them ( 1 2+) has been crystalized and isolated. SQUID measurements, single crystal X‐ray diffraction and theoretical calculations show 1 2+ has unexpected non‐Kekulé diradical character, sharply different from o‐quinodimethane. 相似文献
6.
Michael Schmittel Jens-Peter Steffen Bernd Engels Christian Lennartz Michael Hanrath 《Angewandte Chemie (International ed. in English)》1998,37(17):2371-2373
The regioselectivity of the biradical cyclization of enyne-carbodiimides 1 can easily be controlled by variation of R1 at the alkyne terminus. Attachment of a hydrogen atom (R1=H) leads to C2–C7 cyclization and formation of biradical 2 , whereas C2–C6 cyclization to provide biradical 3 is observed with R1=Me3Si or Ph. 相似文献
7.
Olaf Schmidt Andr Fuchs Dietrich Gudat Martin Nieger Wilfried Hoffbauer Edgar Niecke Wolfgang W. Schoeller 《Angewandte Chemie (International ed. in English)》1998,37(7):949-952
The butadiene-like phosphanylcarbene 2 is, according to ab initio calculations, the intermediate in the conversion of 1 into 3 in the solid state [Eq. (a)]; it is only 1.3 kJ mol−1 higher in energy than 1 . For this conversion, only minor changes in the endocyclic bonds are required throughout the entire reaction. R2N=2,2,6,6-Me4C5H6N. 相似文献
8.
Michael Schmittel Jens-Peter Steffen Miguel . Wencesla ngel Bernd Engels Christian Lennartz Michael Hanrath 《Angewandte Chemie (International ed. in English)》1998,37(11):1562-1564
Both benzocarbazoles and quinolines can be synthesized from enyne ketenimines 1 generated in situ via biradical intermediates (see reaction below). Which of the heterocyclic ring systems is formed depends on the choice of the substituent R1 at the alkyne terminus. 相似文献
9.
Andre Fuchs Martin Nieger Edgar Niecke Laszlo Nyulaszi Olaf Schmidt Wolfgang Schoeller 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1605-1608
1,3-Diphosphetane-2,4-diyles ( A ) possess a diradical molecular structure. Experimental studies reveal interconversions of different valence isomers of the diradicals. As a consequence of the facile thermal ring opening of 1,3-diphosphetane-2.4-diyles A , we obtained crypto-phosphinocarbenes ( B ), confirmed by the results of intramolecular rearrangements as well as reactions with multiple bonded systems. A new range of five- and six-membered phosphorus heterocycles are isolated, including transition-metal complexes. The mechanism for the ring-expansion are predicted by quantum chemical calculations. 相似文献
10.
Dr. Shinobu Arikawa Dr. Akihiro Shimizu Dr. Daisuke Shiomi Prof. Dr. Kazunobu Sato Prof. Dr. Takeji Takui Dr. Hikaru Sotome Prof. Dr. Hiroshi Miyasaka Dr. Masahito Murai Prof. Dr. Shigehiro Yamaguchi Prof. Dr. Ryo Shintani 《Angewandte Chemie (International ed. in English)》2023,62(29):e202302714
A kinetically-stabilized nitrogen-doped triangulene cation derivative has been synthesized and isolated as the stable diradical with a triplet ground state that exhibits near-infrared emission. As was the case for a triangulene derivative we previously synthesized, the triplet ground state with a large singlet-triplet energy gap was experimentally confirmed by magnetic measurements. In contrast to the triangulene derivative, the nitrogen-doped triangulene cation derivative is highly stable even in solution under air and exhibits near-infrared absorption and emission because the alternancy symmetry of triangulene is broken by the nitrogen cation. Breaking the alternancy symmetry of triplet alternant hydrocarbon diradicals by a nitrogen cation would therefore be an effective strategy to create stable diradicals possessing magnetic properties similar to the parent hydrocarbons but with different electrochemical and photophysical properties. 相似文献