ライフサイエンスコーパス: open-shell

1 The open-shell 2-OS also exhibited a large two-photon absorp

2 Luminescence of open-shell 3d metal complexes is often quenched due to u

3 tners such as alcohols, which undergo facile open-shell activation via photocatalysis.

4 The stabilization of these open-shell Al-Mg clusters is proposed to originate from

5 ibe tetrafluorenofulvalene (TFF), a twisted, open-shell alkene for which these general rules do not h

6 H surfaces may even allow the preparation of open-shell alkyl radical dimers (and possibly polymers)

7 The hexaradicaloid, which combines open-shell and macrocyclic contributions to its n conjug

8 ed machine learning framework for simulating open-shell anions and cations.

9 theorized to contain a contribution from its open-shell aromatic singlet diradical form.

10 The open-shell benzoylnitrene radical anion, readily generat

11 rgy gap of 0.27 eV and exhibits a pronounced open-shell biradical character close to 1 (y(0) = 0.92).

12 pi-conjugated systems with low band gap and open-shell biradical character.

13 BN exists as both flat closed-shell and bent open-shell biradical conformers, which interchange by th

14 ed-shell quinoidal structure for 1-CS and an open-shell biradical form for 2-OS.

15 osed shell (formally Ti(IV) enolates) and an open shell, biradical, singlet (formally Ti(III) enolate

16 Recent advances in open-shell biradicaloids have shown that the number of a

17 report the synthesis of the first terminal, open-shell carbide complexes, [K][1] and [1][BAr(F)(4)]

18 open-shell variants are very limited, and an open-shell carbide has yet to be reported.

19 The design of open-shell carbon-based nanomaterials is at the vanguard

20 redox states, as well as a series of related open-shell carbyne complexes.

21 ncement effect allowed for quantification of open-shell catalytic intermediates in real time during t

22 The open-shell catalytically active species, like radical ca

23 The use of a molecular open-shell cation is presented here as a possible reacti

24 +) cluster, which is the first example of an open-shell cationic B(12) cluster in which the unpaired

25 The open-shell cationic stannylene-iron(0) complex 4 (4=[(Ph

26 he gas phase even for the charge states with open shell character.

27 Furthermore, D-A polymers with open-shell character display higher dielectric constant

28 c structures, however, studies have revealed open-shell character emanating from design paradigms suc

29 The open-shell character is retained at room temperature, an

30 Interestingly, tridecacene's open-shell character is significantly reduced upon inter

31 he detection and sophisticated tuning of the open-shell character of individual diradicals with a don

32 a combination of nonbenzenoid topologies and open-shell character should have wide implications in ha

33 nthracene framework that exhibits pronounced open-shell character yet possesses remarkable stability.

34 by computational investigations, reveal the open-shell character, that is, the antiferromagnetic sin

35 In line with its open-shell character, the coronoid has a small electroni

36 Notably, the dianion has an open-shell character, whereas the dication has a closed-

37 tant atom and product diatomic molecule have open-shell character, which introduces the intriguing co

38 al potential to avoid self-immolation of the open-shell character.

39 systems often suffer from poor ground-state open-shell characters necessary to realize a stable grou

40 that maximize charge transfer in all of the open-shell chemistries investigated.

41 Buk2 folds like an open-shelled clam, with each of the two domains represen

42 clusters and the spin-allowed reactions with open-shell clusters to give singlet [M(x)(+)...O2(2-)](-

43 ence on the existence of unexpectedly stable open-shell clusters, which are more stable than their cl

44 Using the example of open-shell complexes derived from platinum and a 1,4-ter

45 Open-shell compounds bearing metal-carbon triple bonds,

46 al and the unpaired electrons present in the open-shell configuration of a charge-separated excited s

47 C(13) adopts an open-shell configuration with a triplet ground state and

48 ctrons, corresponding to a Pr (4f(2) 6s(1) ) open-shell configuration.

49 l entanglement vanishes unless opposite-spin open shell configurations are present in the wavefunctio

50 Such highly open-shell configurations are labeled as hyper open-shel

51 take into account, whenever possible, hyper open-shell configurations as well.

52 g the recent decades, it has been shown that open-shell coordination compounds may exhibit intramolec

53 This recognition of sugar derivatives by open-shell CTV-based host compounds is unprecedented and

54 a series of positively charged polycationic open-shell cyclophanes.

55 nclude wide-gap oxides, compounds containing open-shell d electrons, and compounds made of heavy elem

56 ations, whereas ferromagnetic order requires open-shell d(n) configurations with unpaired electrons.

57 pectra of cyclopentadithiophene-based closed/open-shell D-A polymers using density functional theory

58 l gold nanosphere oligomers, corroborated by open-shell density functional theory calculations.

59 ossbauer spectroscopy, magnetochemistry, and open-shell density functional theory.

60 a copper metallaphotoredox manifold for the open shell deoxygenative coupling of alcohols with N-nuc

61 rmation that interchanges "closed-shell" to "open-shell" descriptions.

62 In this work, we report neutral open-shell di- and polyradical conjugated materials exhi

63 ganic systems, such as those with the highly open-shell diiron active sites.

64 underlying magnetic coupling in closed- and open-shell dinuclear complexes is described using a pert

65 ion at boron through a transition state with open-shell diradical character.

66 the single-molecule conductance of a neutral open-shell diradical compound, a [2,1-b] isomer of inden

67 onic structure combining singlet carbene and open-shell diradical features.

68 The resulting .OOH of the open-shell diradical pair is placed in an optimal positi

69 oaromatic nature that evolves aromaticity in open-shell diradical resonance structures.

70 -state electronic structure of 1(+) to be an open-shell diradical singlet state with antiferromagneti

71 s exist molecules that by design can support open-shell diradical structures.

72 Besides reversible switching between an open-shell diradical- and a closed-shell electronic conf

73 diates can adopt either closed-shell (CS) or open-shell-diradical (OS) singlet ground states.

74 In this work, we have used open-shell dispersion-corrected DFT calculations, quasi-

75 a conical intersection have closed-shell and open-shell dominant configurations correlating with the

76 tunable molecular wire platform comprised of open-shell donor-acceptor macromolecules that exhibit re

77 The measured rate differences between the open-shell Dy(3+) and closed-shell Y(3+) complexes demon

78 of novel chemoselective transformations via open-shell electron pathways.

79 t the key phenoxyl intermediate serves as an open-shell electron-withdrawing group in these reactions

80 Open-shell electronic configurations facilitate strong f

81 en-shell configurations are labeled as hyper open-shell electronic configurations in this work and ar

82 The open-shell electronic nature of the radicals was further

83 ated control of boraphenanthrene closed- and open-shell electronic states, which has led to the first

84 c basis for the transition from a closed- to open-shell electronic structure and connecting the physi

85 radicals, systems with unpaired electrons of open-shell electronic structures, set the stage for a mu

86 lications in electronic devices due to their open-shell electronic structures.

87 pothetical closed-shell systems and that the open-shelled electronic configuration gives rise to the

88 Additionally, all the UAu(6) isomers have open-shell electrons, which in nearly all cases are loca

89 cts by attaching an odd number of addends to open-shell EMFs (such as Sc3 C2 @Ih -C80 ) whereas an ev

90 f radical pyridoxal enzymology by leveraging open-shell enamine catalysis, opening up avenues for dev

91 Macromolecules bearing open-shell entities offer unique transport properties fo

92 The open-shell even-sized Bi(n)(-) clusters are more reactiv

93 Interestingly, for both open-shell Fe(III) complexes, the yields were small (<0.

94 nd subsequent functionalization furnishes an open-shell Fe-diazenido complex.

95 ate energetics that usually assumes ordinary open shells for single-centered radicals needs modificat

96 loids with stable coexisting close-shell and open-shell forms exhibit unconventional self-doping beha

97 state effect in the RPES measurements of the open-shell [Formula: see text] complex.

98 sible to investigate triangulene and related open-shell fragments at the single-molecule level.

99 ent couplings proceeding via carbanionic and open shell (free radical) intermediates.

100 ent couplings proceeding via carbanionic and open-shell (free radical) intermediates.

101 ts show thermally activated behavior for the open-shell gold complexes, with room temperature conduct

102 dge modification affect spin distribution in open-shell graphene fragments?

103 ggest that the binuclear complex exhibits an open-shell ground electronic state, and reaction kinetic

104 a classical Kekule structure, leading to an open-shell ground state with potential applications in o

105 ng the electrical conductivity and potential open-shell ground states.

106 ry calculations confirm an antiferromagnetic open-shell ground-state electronic configuration for tri

107 These open-shell host compounds were then tested in the recogn

108 ,1-no]tetraphene, the first helically chiral open-shell hydrocarbon, in which one benzene ring is fus

109 (TriBNit), was synthesized as a milestone of open-shell inorganic benzene.

110 selectivity in reactions involving uncharged open-shell intermediates and expand our understanding of

111 litated by the electrophilic nature of these open-shell intermediates and the presence of strong pola

112 t the pyramidal inversion barriers for these open-shell intermediates are on the order of approximate

113 rged as a powerful strategy to tame fleeting open-shell intermediates for stereoselective transformat

114 Excitation with visible light generates open-shell intermediates under mild conditions, includin

115 Studies of the electronic structure support open-shell intermediates, a deviation from traditional s

116 reactivity is difficult for highly reactive open-shell intermediates.

117 hat uses photoexcited lumiflavin to generate open-shell intermediates.

118 n reactions of transient and highly reactive open-shell intermediates.

119 complex electronic structure connecting the open shell iron d-orbitals with three aromatic ring syst

120 Open-shell iron and cobalt alkyl complexes have been syn

121 Coordination to an open-shell iron center leads to complex electronic struc

122 it exalted diamagnetism, evidencing actinide open-shell jellium aromaticity superatom character.

123 Herein, we report such terminal imides of open-shell lanthanide cations Ce(III), Nd(III), and Sm(I

124 rge-separated species with a radical anionic open-shell ligand, [((t-BuArO)3tacn)UIV(eta2-NNCPh2)] (2

125 Open-shell macromolecules (i.e., polymers containing rad

126 ghlight vital developments in the history of open-shell macromolecules to explain the current state o

127 k to address where it seems most likely that open-shell macromolecules will go in the coming years.

128 Open-shell materials bearing multiple spin centres provi

129 lecular homolytic substitution (S(H)2) is an open-shell mechanism that is implicated across a host of

130 plex provides a highly unusual example of an open-shell metal complex that binds dihydrogen as a liga

131 loits the metal-centered radicals present in open-shell metal complexes as one-electron catalysts for

132 ploits the metal-centred radicals present in open-shell metal complexes as one-electron catalysts for

133 Geminate charge recombination in open-shell metal complexes, such as the two Fe(III) phot

134 is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand.

135 II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through mu

136 ient design strategy opens access to neutral open-shell mixed-valence species via the redox transform

137 f Lewis and Bronsted acids, resulting in the open-shell Mn(IV)(O)(TBP8Cz(*+)):LA (LA = Zn(II), B(C6F5

138 The study of open-shell molecules has been rekindled in recent years

139 However, prior syntheses of ambient stable, open-shell molecules required lengthy routes and display

140 Neutral open-shell molecules, in which spin density is delocaliz

141 w hydrocarbon structures, including reactive open-shell molecules.

142 he closed-shell La2 @Ih -C80 forms a stable, open-shell monoadduct instead of the anticipated closed-

143 the Ta(V) hydrazido chloride 1 generates the open-shell, mononuclear Ta(IV) hydrazido complex 2, whic

144 Fully optimized unrestricted open-shell MP2 calculations for the lowest-energy triple

145 The reactions afford the synthesis of two open-shell nanographenes (1a and 1b) exhibiting differen

146 ach, we report the synthesis of nonbenzenoid open-shell nanographenes containing two pairs of embedde

147 Our work provides unprecedented access to open-shell nanographenes with high-spin ground states, p

148 to arene structures and synthesis of larger, open-shell nanographenes.

149 emical description is difficult due to their open shell nature and low-lying excited electronic state

150 quantum chemical calculations support their open-shell nature and provide further insights into thei

151 and selective for epoxidation because of the open-shell nature of their electronic structure.

152 l organic mixed-valence compounds due to the open-shell nature of their electronic structure.

153 e are minimal energy differences between the open-shelled NCs and hypothetical closed-shell systems a

154 redictions indicate that the largest MEC for open-shell NGs occurs in proximity to the transition bet

155 Open-shell non-alternant polycyclic hydrocarbons (PHs) a

156 report the synthesis and characterization of open-shell octairon clusters supported by two heptaamine

157 rs of numerous hydrolytic enzymes due to the open shell of boron, which allows it to expand from a tr

158 ns in this work and are compared to ordinary open-shell or closed-shell electronic configurations.

159 Open shell organic molecules bearing n-cores are of grea

160 At present, most luminescent open-shell organic molecules are pai-diradicals, but suc

161 iples database (Rad-6) containing closed and open-shell organic molecules, along with an associated d

162 Open-shell organic molecules, including S = 1/2 radicals

163 Chichibabin's hydrocarbon as a classical open-shell PAH has been investigated for a long time.

164 bons (PAHs) and open up a new avenue towards open-shell PAHs with prominent singlet biradical charact

165 as well as computational studies, reveal the open-shell pai-arene complex to have a BDFE(C-H) value o

166 abilizing unpaired spin in the ground state, open-shell pai-conjugated molecules can achieve optoelec

167 uorene exhibits one of two ground states: an open-shell pai-diradical state, predicted to be a triple

168 Open-shell, pai-conjugated molecules represent exciting

169 (PTEO), a nonconjugated polymer with stable open-shell pendant groups, facilitated better electron e

170 nobelt through the self-assembly of spin-one open-shell perylene diimide diradical anions (:PDI(2-))

171 Open-shell phenalenyl chemistry has widely been explored

172 Open-shell phenalenyl chemistry started more than half a

173 e, we have explored another new direction of open-shell phenalenyl chemistry toward transition metal-

174 te of the methoxyphenylcarbene will resemble open-shell phenylnitrene, which is known to undergo ring

175 Of particular note has been work with open-shell photocatalysts, which tend to have comparativ

176 sis is readily amenable to the generation of open-shell photocatalysts, which tend to have exceptiona

177 s offers a new route to create non-alternant open-shell PHs with high-spin ground states, and opens u

178 y of such non-Kekule hydrocarbons results in open-shell pi-conjugated graphene fragments that give ri

179 's hydrocarbon occupies a central role as an open-shell platform for new organic materials, however l

180 Stable open-shell polycyclic aromatic hydrocarbons (PAHs) are o

181 ved synthetic strategies, the engineering of open-shell porphyrinoid polymers with spin delocalizatio

182 iones, which could serve as phenalenyl-based open-shell precursors, can be synthesized.

183 ce that pai-extended triangulene retains its open-shell quartet ground state on the surface.

184 ike 1S(2)1P(6) electron configuration to the open-shell radical 1S(2)1P(5) and diradical 1S(2)1P(4) c

185 ll neutral and charged molecules, 13 million open-shell radical configurations, and 200K radical reac

186 tions demonstrate a surprising prevalence of open-shell radical intermediates, and that the redox che

187 rogen-atom transfer (HAT) and proceeding via open-shell radical intermediates, have been expanding ra

188 The stability of the open-shell radical is derived from the basicity of the t

189 Conducting polymers based on open-shell radical moieties exhibit potentially advantag

190 The interactions between open-shell radical species and liquid-phase cloud drople

191 tiaromatic (2(2-)) triad, in addition to the open-shell radical states (2(+), 2(-)).

192 This prevents immediate formation of open-shell (radical) intermediates from the amine upon l

193 ic fragments include unique closed-shell and open-shell (radical) products.

194 rent spin states, making them unsuitable for open-shell reactive chemistry.

195 y, which proceeds in a concerted manner, and open-shell reactivity, which proceeds in a stepwise fash

196 Notably, these open-shell rearrangements demonstrate a vast substrate s

197 s suggest that the process occurs through an open-shell redox manifold at bismuth, comprising three u

198 electronic structure and stability of their open-shell redox states has not been performed previousl

199 arises from bias-dependent alignment of the open-shell resonances.

200 Using the restricted open shell (ROS) method as proposed by Wright and co-wor

201 have afforded "heavy atom" radicals, neutral open-shell (S = 1/2) molecular species containing heavy

202 sed-shell hydrocupration of alkynes with the open-shell single electron transfer (SET) chemistry of t

203 Reactions proceeding through open-shell, single-electron pathways offer attractive al

204 2)(d)() structure and possessing a low-lying open shell singlet state.

205 rate single-electron transfer to generate an open-shell singlet "nitrene-substrate radical, ligand ra

206 tions found F(10)(2-), for example, to be an open-shell singlet (<S(2)> approximately 1), with electr

207 nd a small negative charge on Ca and (ii) an open-shell singlet (biradical) at intermediate approach

208 ter in the doubly oxidized ground state: the open-shell singlet (S2 = 0.989) is 3.8 kcal/mol more sta

209 xplained by the barrierless collapse of this open-shell singlet 1,4-biradical.

210 from the 1,1-diazene intermediate to form an open-shell singlet 1,4-biradical.

211 fulven-6-one (13) either concertedly or via open-shell singlet 6-oxocyclohexa-2,4-dienylidene (18).

212 The open-shell singlet and triplet "carbocations" described

213 ing ring-closure (through a MECP between the open-shell singlet and triplet surfaces) or carbon-carbo

214 ogressions in the X(3B) ground state and the open-shell singlet b (1B) state arise from the change in

215 Polycyclic aromatic hydrocarbons with an open-shell singlet biradical ground state are of fundame

216 ry studies show that these compounds have an open-shell singlet biradical ground state with a thermal

217 -TIPS with a smaller energy gap exists as an open-shell singlet biradical with a large measured birad

218 heterocyclopentanediyl isomer represents an open-shell singlet biradical with interesting photochemi

219 Calculated reaction barriers for an open-shell singlet biradical-mediated stepwise [1,5] sig

220 The Group 15 open-shell singlet biradicaloid [P(mu-NTer)]2 (Ter=2,6-b

221 oaches reveal that the diborete possesses an open-shell singlet biradicaloid ground state, which is s

222 and, to our knowledge, no other examples of open-shell singlet carbocations.

223 itous, biradical 4 represents a rare type of open-shell singlet compound with 95% biradical character

224 For certain donor-acceptor frameworks, an open-shell singlet configuration is the computed ground

225 Open-shell singlet configurations ((1)A(2), (1)B(1), (1)

226 le diisonitriles, even the catenation of two open-shell singlet cyclopentane-1,3-diyls is achieved.

227 species thermally equilibrate, reforming the open-shell singlet cyclopentanediyl.

228 m ions, but spectroscopic evidence favors an open-shell singlet diradical assignment for the observed

229 ation with NO.SbF(6), all displaying unusual open-shell singlet diradical character with a small sing

230 x undergoes intersystem crossing to form the open-shell singlet diradical complex before it forms the

231 nonacene skeleton, effectively converting an open-shell singlet diradical into a closed-shell system.

232 The dication ABA(2+) and dianion ABA(2-) are open-shell singlet diradicaloids, while the longer dicat

233 anisms and offer a new strategy to stabilize open-shell singlet diradicals.

234 (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a

235 ground-state wave function that has both an open-shell singlet f(13)(pi*)(1), where pi* is the lowes

236 l occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a varie

237 in solution shows a low optical gap, and an open-shell singlet ground state with a low singlet-tripl

238 actions (2J = -118 J.mol(-1)), supporting an open-shell singlet ground state with a thermally accessi

239 They also show open-shell singlet ground states according to electron p

240 diradical character of up to 77% and possess open-shell singlet ground states with thermally accessib

241 abin hydrocarbon (p,p'-biphenylene bridged), open-shell singlet is the ground state.

242 The reactivities of open-shell singlet oxyallyls (1)9a-e determine the produ

243 Support for an open-shell singlet species was obtained by spectroscopic

244 If a biradical intermediate, such as the open-shell singlet state of alpha,3-didehydrotoluene (4)

245 ple bond completes bond formation through an open-shell singlet transition state that formally reduce

246 is reaction occurs preferentially through an open-shell singlet transition state: iron donates electr

247 rned by the ground triplet state because the open-shell singlet with the unpaired electrons localized

248 In this open-shell singlet, the ligand-mediated antiferromagneti

249 nium ions have low-energy open-shell states (open-shell singlet, triplet) due to stabilization of a p

250 to generate an intermediate with close-lying open-shell singlet, triplet, and closed-shell singlet el

251 e of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupl

252 en-shell triplet diradical with a very small open-shell singlet-triplet energy gap that is indicative

253 hose ground states are multiconfigurational, open-shell singlets in which ytterbium is intermediate v

254 In solutions, both stereoisomers exist as open-shell singlets with DeltaE(S-T) = -3.1 and -3.8 kca

255 e measurements reveal that our materials are open-shell singlets with different degrees of spin inter

256 n alternative pathway involving attack of an open shell species generated from the alkyl halide to a

257 the analysis of the electronic properties of open-shell species and has potential applications in a w

258 In addition, with light, open-shell species can be generated which open up new re

259 This database of open-shell species entails frequently encountered synthe

260 ived transient nature of these doublet state open-shell species has led to debatable mechanistic stud

261 In addition, boron-centered open-shell species with S > 1/2 have emerged as attracti

262 cance to a wide array of reactions involving open-shell species.

263 , magnetic, and thermoelectric properties of open-shell species.

264 r, which is also a unique observation for an open-shell species.

265 he first conformational photoswitching of an open-shell species.

266 Integrating radical (open-shell) species into non-cryogenic nanodevices is ke

267 ible one-electron reduction, suggesting that open-shell stannylidyne complexes might be accessible us

268 of the chromophores remain preserved in the open shell state and match the ones of the pristine pare

269 two-step chemical procedure to preserve the open-shell state and hence the electroactivity of the ni

270 l as it can be utilized to create an in situ open-shell state by external spin injection.

271 bstituted phenyloxenium ions have low-energy open-shell states (open-shell singlet, triplet) due to s

272 The hyper open-shell states considered in this work are especially

273 Maintaining and stabilising multiple open-shell states-especially in contact with metallic el

274 s of the transition between closed-shell and open-shell states.

275 y to the transition between closed-shell and open-shell states.

276 The requisite intersystem crossing in the open-shell structure is accompanied by structural reorga

277 be described as either a closed-shell or an open-shell structure on the basis of their molecular siz

278 etween the central and terminal atoms and an open-shell structure with a single bond and two lone ele

279 certain molecular topologies may lead to an open-shell structure.

280 esized diradicaloid in the search for stable open-shell structures, but it remains sensitive to oxyge

281 for quantifying the electronic properties of open-shell substituents based on changes in nitrile vibr

282 of inductive and resonance effects in these open-shell substituents.

283 B[4,5], and C[4,3]), which are the smallest open-shell systems in their respective chemical families

284 Open-shell systems such as radical intermediates are cen

285 Open-shell systems with extensive pai-conjugation have f

286 s, allowing efficient exploration of complex open-shell systems, and significantly advancing our abil

287 nic structure and the NMR chemical shifts in open-shell systems, including the ruthenium-based metall

288 ree benzene rings and belong to the class of open-shell systems.

289 in challenging charge-transfer complexes and open-shell systems.

290 ingle-electron oxidation affords a transient open-shell terminal phosphide cation with significant sp

291 ing the scaffold protein was excluded, large open shells that did not attain icosahedral structure we

292 eory, which showed a transition from singlet open-shell to closed-shell configuration.

293 An open-shell transition metal like iron or copper is emplo

294 rast to the digallenes, addition involves an open-shell transition state consistent with the higher s

295 Computations are consistent with an open-shell triplet diradical with a very small open-shel

296 switched electrochemically with the neutral open-shell triplet state with orthogonal conformation, w

297 oach (UBLYP) with a 6-31G* basis set for the open-shell triplet states of the reactants, products, an

298 abundance of closed-shell carbynes reported, open-shell variants are very limited, and an open-shell

299 closed-shell electron configurations, but an open-shell variation with jellium aromaticity has been p

300 nistic and computational studies confirm the open-shell, zwitterionic nature of the self-doped state