Aggregation‐Induced Emission and Aggregation‐Promoted Photo‐oxidation in Thiophene‐Substituted Tetraphenylethylene Derivative

Aggregation‐induced emission combined with aggregation‐promoted photo‐oxidation has been reported only in two works quite recently. In fact, this phenomenon is not commonly observed for AIE‐active molecules. In this work, a new tetraphenylethylene derivative (TPE‐4T) with aggregation‐induced emission (AIE) and aggregation‐promoted photo‐oxidation was synthesized and investigated. The pristine TPE‐4T film exhibits strong bluish‐green emission, which turns to quite weak yellow emission after UV irradiation. Interestingly, after solvent treatment, the weakly fluorescent intermediate will become bright‐yellow emitting. Moreover, the morphology of the TPE‐4T film could be regulated by UV irradiation. The wettability of the TPE‐4T microcrystalline surface is drastically changed from hydrophobic to hydrophilic. This work contributes a new member to the aggregation induced photo‐oxidation family and enriches the photo‐oxidation study of tetraphenylethylene derivatives.     

N-[ω-(三丁基锡甲氧基)烷基]邻苯二甲酰亚胺的合成及其光环化反应

烷基二醇与三丁基锡碘甲烷反应得三丁基锡甲氧基烷基醇(2a~2 e);2(或其衍生物)与邻苯二甲酰亚胺反应合成了N-[ω-(三丁基锡甲氧基)烷基]邻苯二甲酰亚胺(5a~5 e),其结构经NMR和MS表征。5在光诱导下,由单电子转移引发,经分子内自由基偶合,高产率(85%~99%)地获得可控制反应位置的大环化合物。     

Total Synthesis of (+)‐ and (−)‐Decursivine and (±)‐Serotobenine through a Cascade Witkop Photocyclization/Elimination/Addition Sequence: Scope and Mechanistic Insights

In this article, the total syntheses of antimalarial compound decursivine and its biologically inactive sibling serotobenine are presented. The biomimetic synthesis of (±)‐serotobenine was investigated first, but failed. During the subsequent investigation of other synthetic routes, we discovered a new cascade Witkop photocyclization/elimination/addition sequence, which enabled the expedient synthesis of not only racemic decursivine and serotobenine, but also enantiopure (+)‐ and (?)‐decursivine and a variety of their analogues. The present syntheses represent the shortest pathway for the total synthesis of decursivine and serotobenine to date. Moreover, the newly developed cascade sequence for the total synthesis of decursivine does not need any protecting steps. The scope and the reaction mechanism of the cascade sequence were also studied. A rational mechanism for the cascade sequence is proposed, which is consistent with the previous studies and our current experimental results.     

Contorted Heteroannulated Tetraareno[a,d,j,m]coronenes

Fused polycyclic aromatic compounds are interesting materials for organic electronics applications. To fine-tune photophysical or electrochemical properties, either various substituents can be attached or heteroatoms (such as N or S) can be incorporated into the fused aromatic backbone. Coronenes and heterocoronenes are promising compounds in this respect. Up until now, the possibilities for varying the attached fused heteroaromatics at the coronene core were quite limited, and realizing both electron-withdrawing and -donating rings at the same time was very difficult. Here, a series of pyridine, anisole and thiophene annulated tetraareno[a,d,j,m]coronenes has been synthesized by a facile two-step route that is a combination of Suzuki-Miyaura cross-coupling and a following cyclization step, starting from three different diarenoperylene dibromides. The contorted molecular π-planes of the obtained cata-condensed tetraarenocoronenes were analyzed by single-crystal X-ray crystallography, and the photophysical and electrochemical properties were systematically investigated by UV/Vis spectroscopy and cyclovoltammetry.     

Photochromism of dihydroindolizines part VII: multiaddressable photophysical properties of new photochromic dihydroindolizines bearing substituted benzo[i]phenanthridine as a fluorescing moiety

Sixteen benzo[i]phenanthridine derivatives 8a‐p were prepared via photocyclization of cis‐trans substituted 4‐styrylquinolines in low‐to‐moderate yields. The chemical structure of the photocyclized benzo[i]phenanthridine derivatives was unambiguously elucidated by means of both spectral and analytical tools. The photochromic (PC) dihydroindolizines (DHIs) 8a‐p based on benzo[i]phenanthridines were prepared in 19–57% yields via nucleophilic addition of benzo[i]phenanthridines 4a‐p to spirocyclopropenes 5 . The 1D, 2D, NOESY NMR spectra, mass spectrometry, and elemental analysis were used for characterization of the chemical structures of the newly synthesized DHIs 8a‐p . Developing and tuning of the photophysical properties of the synthesized compounds by substituents in the base part have been achieved. The absorption maxima (λ_max) and the half‐lives (t_1/2) of the colored zwitterionic forms 7a‐p were detected in all cases by flash‐photolysis measurements due to the fast 1,5‐electrocyclization back to the DHI system. Irradiation of DHI 8a‐p in'CH₂Cl₂ solution with polychromatic light leads to the formation of green to green–blue colored betaines 7a‐p after cooling with liquid nitrogen. The kinetics of the fast bleaching process of betaines 7a‐p to DHIs 8a‐p , studied by flash photolysis as well as low temperature FT‐UV/VIS, were found to take place in the millisecond range (432–2675 ms) in dichloromethane solution and fitted well a first‐order thermal back reaction. The fluorescence spectra as well as the fluorescence quantum yield were studied. Noticeable bathochromic and hypsochromic shifts in the emission spectra by changing the substituents in the base part were monitored. Interestingly, the photo‐fatigue resistance of some studied betaines 7a‐p showed a higher t₃₀‐value than the standard one (dicyanopyridazine DHI). Large solvatochromic effects on the absorption maxima (λ_max) as well as a substantial increase in the half‐lives (t_1/2) with solvent polarity of betaines 7a‐p were also observed. The multiaddressable PC properties of DHIs 8a‐p will help these compounds to find applications. Copyright © 2007 John Wiley & Sons, Ltd.     

Aggregation-Induced Emission of Triphenyl-Substituted Tristyrylbenzenes

The synthesis, properties and X-ray single-crystal structures of two regioisomeric triphenyl tristyrylbenzenes are reported. Both C_3v and C_s derivatives display aggregation-induced emission (AIE) behavior. Regioisomerism impacts the solid-state intermolecular interactions, the photophysical characteristics and photostability in solution.     

Synthesis of [7]Helicene Enantiomers and Exploratory Study of Their Conversion into Helically Chiral Iodoarenes and Iodanes

The facile and convenient preparation of both enantiomers of a [7]helicene scaffold from inexpensive (l )-(+)-tartaric acid and 4-methylstyrene is described. These helical structures were transformed into bis-iodinated ether derivatives in order to explore their potential as precursors of novel chiral organoiodane reagents or as iodoarene pre-catalysts. Promising results were obtained in hydroxylative phenol dearomatization/[4+2] cycloaddition cascade and dearomative spirolactonization reactions with encouraging enantiomeric excesses.     

Regulation of an Ambient-Light-Induced Photocyclization Pathway (Norrish–Yang Versus 6π) by Substituent Choice

Photocyclization, irrespective of whether multiple steps (e.g., Norrish–Yang cyclization) or a single concerted step (e.g., 6π photocyclization) are involved, is an intramolecular photochemical process resulting in the formation of one new single bond to afford a ring system. In particular, visible-light-induced photocyclization offers a green and sustainable route to organic cyclic compounds that are difficult to access by thermal reactions. Herein, we describe the ambient light-induced intramolecular photocyclization of a series of donor/acceptor chromophores 1 d – 3 d containing two types of photoresponsive motifs, namely an electron-deficient BF₂-chelated ketone fused with an electron-rich thiophene, and probe the solution-phase and solid-state photochromic performance of these compounds. The results reveal that simple variation of R substituents on the diaryl moiety allows one to control the intramolecular photocyclization mechanism with high photochemical selectivity, e.g., under ambient light, methyl-substituted 1 d and 2 d undergo reversible 6π photocyclization, whereas ethyl-substituted 3 d exclusively undergoes irreversible Norrish–Yang photocyclization. Single-crystal X-ray analysis of Norrish–Yang cyclization products reveals the formation of four pairs of conformational enantiomers differing in the dihedral angle between benzothiophene and the BF₂ core, namely (±) N -3 d @68°, (±) N -3 d @-77°, (±) N -3 d @-78°, and (±) N -3 d @-102°. The UV/Vis absorption spectra of 1 d – 3 d cover a broad visible-light region (380–572 nm), while DFT and TD-DFT calculations reveal that absorption in this region is dominated by the charge-transfer (CT) transition from the thiophene-centered HOMO to the LUMO of the electron-deficient π-conjugated BF₂-chelated unit and the n→π* and π→π* transitions within the latter unit. The spatial separation of the HOMO and LUMO of these dyes promotes triplet-state generation and self-photosensitizes intramolecular photocyclization in the visible-light region. Three-dimensional time-resolved and steady-state emission spectra of 3 d show that the Norrish–Yang photocyclization takes place within milliseconds with excellent conversion efficiency (96 %).     

A Photoinduced Cyclization Cascade—Total Synthesis of (−)‐Leuconoxine

A protecting‐group‐free and enantioselective total synthesis of the monoterpenoid indole alkaloid (?)‐leuconoxine was accomplished. The key step comprises a novel photoinduced domino macrocyclization/transannular cyclization involving the Witkop cyclization, for which additional mechanistic evidence is provided. This process furnishes a diaza[5.5.6.6]fenestrane skeleton, which is a hitherto unprecedented structure element.