13029-09-9Relevant articles and documents
A silicon-heteroaromatic system as photosensitizer for light-driven hydrogen production by hydrogenase mimics
Goy, Roman,Apfel, Ulf-Peter,Elleouet, Catherine,Escudero, Daniel,Elstner, Martin,Goerls, Helmar,Talarmin, Jean,Schollhammer, Philippe,Gonzalez, Leticia,Weigand, Wolfgang
, p. 4466 - 4472 (2013)
The utilization of light and inexpensive catalysts to afford hydrogen represents a huge challenge. Following our interest in silicon-containing [FeFe]-hydrogenase ([FeFe]-H2ase) mimics, we report a new model approach for a photocatalytic [FeFe]-H2ase mimic 1, which contains a 1-silafluorene unit as a photosensitizer. Thereby, the photoactive ligand is linked to the [2Fe2S] cluster through S-CH2-Si bridges. Photochemical H2 evolution experiments were performed and revealed a turnover number (TON) of 29. This is the highest reported photocatalytic efficiency for an [FeFe]-H2ase model complex in which the photosensitizer is covalently linked to the catalytic center. We report a viable synthetic pathway for the construction of a new photoactive model of the [FeFe]-hydrogenase ([FeFe]-H2ase) active site with a dithiolate bridge and 1-silafluorene as a photosensitizer. The [FeFe]-H2ase mimic represents a very compact, easily accessible, and inexpensive photocatalyst for hydrogen generation. Copyright
9-Silafluorene and 9-germafluorene: Novel platforms for highly efficient red phosphorescent organic light-emitting diodes
Liu, Xiang-Yang,Tian, Qi-Sheng,Zhao, Danli,Ran, Quan,Liao, Liang-Sheng,Fan, Jian
, p. 8144 - 8151 (2018)
Two novel heterofluorene motifs consisting of the group 14 elements Si and Ge were developed as robust molecular platforms for the construction of organic light-emitting diode (OLED) materials. These two compounds exhibited similar photophysical properties, thermal stabilities and electrochemical behaviors except for the charge transport abilities. The red OLED hosted by a 9-silafluorene derivative (DPS) with Ir(MDQ)2(acac) as the emitter exhibited state-of-the-art current efficiency, power efficiency, and external quantum efficiency (EQE) with maxima of 50.7 cd A-1, 44.7 lm W-1, and 28.3%, respectively. In addition, the maximum EQE of a 9-germafluorene derivative (DPG)-based red device could reach 20%. These results indicated the great potential of group 14 element derivatives in the construction of highly efficient OLED materials.
Transition-Metal-Free Approach for the Direct Arylation of Thiophene: Experimental and Theoretical Investigations towards the (Het)-Aryne Route
Demangeat, Catherine,Saied, Tarak,Ramozzi, Romain,Ingrosso, Francesca,Ruiz-Lopez, Manuel,Panossian, Armen,Leroux, Frédéric R.,Fort, Yves,Comoy, Corinne
, p. 547 - 556 (2019)
This paper presents the results of our investigations on the arylation of thiophene using the transition-metal-free “aryne coupling” methodology. The reaction was studied by both experiment and computation (density functional theory) and comparison with phenyllithium was established. In parallel, the effects of the ligand and the salt on the coupling reaction were examined. The results underline the remarkable effect of such additives on the coupling reaction and the potency of the method to construct hetaryl–aryl backbones which open up promising access to a wide range of heterobiaryl structures using the novel “Het-Aryne” route.
On-surface synthesis of planar acenesviaregioselective aryl-aryl coupling
Feng, Lin,Wang, Tao,Jia, Hongxing,Huang, Jianmin,Han, Dong,Zhang, Wenzhao,Ding, Honghe,Xu, Qian,Du, Pingwu,Zhu, Junfa
, p. 4890 - 4893 (2020)
The reaction of 2,2'-dibromo-biphenyl on a Ag(111) surface leads to the formation of planar acenes with a high-regioselectivity rather than nonplanar saddle-shaped tetraphenylene as the typical product in solution chemistry. The regioselective aryl-aryl coupling reaction is attributed to the hydrogen repulsion between the reactants on the confined two-dimensional surface.
REGIOSELECTIVE DIMETALLIERUNG VON AROMATEN. BEQUEMER ZUGANG ZU 2,2'-DISUBSTITUIERTEN BIPHENYLDERIVATEN
Neugebauer, Wolfgang,Kos, Alexander J.,Schleyer, Rague
, p. 107 - 118 (1982)
Lithiation of biphenyl with 2.4 mol of n-butyllithium in the presence of TMEDA led directly to the 2,2'-dilithio derivative (I) in modest, but preparatively useful yields.I, in turn, was converted to a variety of products.The activation of the 2'-position of 2-lithiobiphenyl was shown directly by a separate experiment.MNDO calculations indicate stabilization in I by double bridging and in 2-lithiobiphenyl by intramolecular ? interaction of Li with the o-phenyl group.Similar interactions in substitution transition states rationalize the specificity of the reactions observed.
Direct Observation of Aggregation-Induced Emission Mechanism
Corminboeuf, Clémence,Guan, Jianxin,Han, Han,Lin, Kun-Han,Liu, Jitian,Peng, Jie,Prlj, Antonio,Wei, Rong,Yu, Zhihao,Zhao, Dahui,Zheng, Junrong
, p. 14903 - 14909 (2020)
The mechanism of aggregation-induced emission, which overcomes the common aggregation-caused quenching problem in organic optoelectronics, is revealed by monitoring the real time structural evolution and dynamics of electronic excited state with frequency and polarization resolved ultrafast UV/IR spectroscopy and theoretical calculations. The formation of Woodward–Hoffmann cyclic intermediates upon ultraviolet excitation is observed in dilute solutions of tetraphenylethylene and its derivatives but not in their respective solid. The ultrafast cyclization provides an efficient nonradiative relaxation pathway through crossing a conical intersection. Without such a reaction mechanism, the electronic excitation is preserved in the molecular solids and the molecule fluoresces efficiently, aided by the very slow intermolecular charge and energy transfers due to the well separated molecular packing arrangement. The mechanisms can be general for tuning the properties of chromophores in different phases for various important applications.
Efficient construction of biaryls and macrocyclic cyclophanes via electron-transfer oxidation of Lipshutz cuprates
Miyake, Yoshihiro,Wu, Mo,Rahman, M. Jalilur,Kuwatani, Yoshiyuki,Iyoda, Masahiko
, p. 6110 - 6117 (2006)
An efficient method for the homocoupling of aryl halides by electron-transfer oxidation of Lipshutz cuprates (Ar2Cu(CN)Li 2) with organic electron acceptors is disclosed. Thus, various types of Lipshutz cuprates are prepared by successive treatment of aryl or heteroaryl bromides with tert-butyllithium and CuCN. The electron-transfer oxidation of Lipshutz cuprates with p-benzoquinones proceeds smoothly to afford the corresponding homocoupling products in moderate to good yields. Furthermore, it can be applied to the construction of either thiophene- or benzene-fused 10-membered ring cyclophanes. For the synthesis of 10-membered cyclophanes, the linear C-Cu-C structure of Lipshutz cuprates should be maintained in the dimetallacyclic intermediates, producing the large ring cyclophanes efficiently. The X-ray analysis of the cyclophanes reveals that the difference in the bridging atoms results in the different conformations of the macrocyclic rings. Thus, the silicon-bridged cyclophane 5a adopts a D2-symmetric structure with a twisted rhombic arrangement of four thiophene rings, whereas the methylene- and oxygen-bridged cyclophanes 5b and 5c possess C2h- and C2-symmetric structures with chair- and boatlike conformations, respectively. The 1H NMR spectrum of C2-symmetric 5c is temperature-dependent, and the activation energy (ΔG?) for the conformational change is 10.1 kcal/mol.
Pd(OAc)2/PPh3-catalyzed desulfonylative homocoupling of arylsulfonyl chlorides
Zhao, Qiao,Chen, Liangshun,Lang, Hongyue,Wu, Shengying,Wang, Limin
, p. 535 - 538 (2015)
The Pd-catalyzed homodimerization with respect to arylsulfonyl chlorides as an efficient method for the synthesis of biaryls has been developed. This desulfonylative reaction which was performed at reflux in 1,4-dioxane for 4 h under air afforded the desired products in good to excellent yields. The Pd(OAc)2/PPh3-catalyzed desulfonylative homodimerization of arenesulfonyl chlorides as an efficient method for the synthesis of biaryls was described. The corresponding products were obtained in good to excellent yields.
BN-phenanthryne: Cyclotetramerization of an 1,2-azaborine derivative
Mueller, Matthias,Bettinger, Holger F.,Maichle-Moessmer, Caecilia
, p. 9380 - 9383,4 (2014)
Thermolysis of 9-azido-9-borafluorene in heptane solution produces the tetramer of a BN-phenanthryne. The isolation of the self-trapping product provides evidence for the involvement of the BN-aryne in the thermolysis reaction. Its formation may be rationalized by denitrogenation of the azide and ring enlargement. Making a first appearance: A BN-aryne analogous to 9,10-phenanthryne can be formed by thermolysis of the 9-azido-9-borafluorene and can undergo cyclotetramerization.
ortho-Phenylene-Based Macrocyclic Hydrocarbons Assembled Using Olefin Metathesis
Hartley, C. Scott,Kirinda, Viraj C.,Schrage, Briana R.,Ziegler, Christopher J.
, (2020)
While many foldamer systems reliably fold into well-defined secondary structures, higher order structure remains a challenge. A simple strategy for the organization of folded subunits in space is to link them together within a macrocycle. Previous work has shown that o-phenylenes can be co-assembled with rod-shaped linkers into twisted macrocycles, showing an interesting synergy between folding and thermodynamically controlled macrocyclization. In these systems the foldamer units were largely decoupled from each other both conformationally and electronically. Here, we show that hydrocarbon macrocycles, with very short ethenylene linkers, can be assembled from o-phenylenes using olefin metathesis. Characterization by NMR spectroscopy, X-ray crystallography, and ab initio calculations shows that the products are approximately triangular trimer macrocycles with helical o-phenylene corners in a heterochiral configuration. Their photophysics are dominated by the 4,4'-diphenylstilbene moieties, the longest conjugated segments, with further conjugation broken by the twisting of the o-phenylenes.
