- Preparation of symmetric dibromides of 1,10-phenanthroline
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Bromation of 1,10-phenanthroline with Br2 proceeds smoothly in the presence of S2Cl2 and pyridine to give 3,8-dibromo-1,10-phenanthroline in good yield. Bromation of 2,9-dibutoxy-1,10-phenanthroline with Br2 in
- Saitoh, Yutaka,Koizumi, Take-Aki,Osakada, Kohtaro,Yamamoto, Takakazu
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- Photobiological activity of Ru(ll) dyads based on (Pyren-1 -yl)ethynyl derivatives of 1, 10-Phenanthroline
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Several mononuclear Ru(ll) dyads possessing 1, 10-phenanthrollne-appended pyrenylethynylene llgands were synthesized, characterized, and evaluated for their potential in photobiologlcal applications such as photodynamlc therapy (PDT). These complexes interact with DNA via intercalation and photocleave DNA in vitro at submlcromolar concentrations when irradiated with visible light (λirr ≥ 400 nm). Such properties are remarkably sensitive to the position of the ethynylpyrenyl substituent on the 1, 10-phenanthroline ring, with 3-substitutlon showing the strongest binding under all conditions and causing the most deleterious DNA damage. Both dyads photocleave DNA under hypoxic conditions, and this photoactlvity translates well to cytotoxicity and photocytotoxlcity models using human leukemia cells, where the 5- and 3-substituted dyads show photocytotoxiclty at 5-10μM and 10-20μM, respectively, with minimal, or essentially no, dark toxicity at these concentrations. This lack of dark cytotoxicity at concentrations where significant photoactlvity Is observed emphasizes that agents with strong intercalating units, previously thought to be too toxic for phototherapeutic applications, should not be excluded from the arsenal of potential photochemotherapeutic agents under investigation.
- Monro, Susan,Scott, John,Chouai, Abdellatif,Lincoln, Richard,Zong, Ruifa,Thummel, Randolph P.,McFarland, Sherri A.
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- Phenanthroline-Based Molecular Switches for Prospective Chemical Grafting: A Synthetic Strategy and Its Application to Spin-Crossover Complexes
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1,10-Phenanthroline represents a well-known versatile ligand system finding many applications in chemistry, biology, and material science. The properties and thus the use of these molecules are determined by coordinating metal ions and ligand substituents. Advanced ligand systems that, for instance, feature simultaneously an integrated photochrome and a surface anchoring group require the introduction of several differing substituents and the synthesis of asymmetric derivatives. In spite of a long history of the ligand system - and to our great surprise - a general synthetic approach allowing the introduction of differing substituents at positions (3,8) and (5,6) of 1,10-phenanthroline is not known. Here, we present a general approach for the synthesis of such phenanthrolines. The approach is used to integrate a diarylethene photochrome into a functionalized phenanthroline and thus to synthesize a novel photoswitchable phenanthroline and a corresponding spin-crossover molecular photoswitch. The functionality of both the ligand and its iron(II) complex at room temperature has been demonstrated. The importance of this work for chemical grafting of molecular switches based on phenanthrolines is emphasized.
- Heinemann, Frank W.,Khusniyarov, Marat M.,Lindner, Thomas,M?rtel, Max,Scheurer, Andreas
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- Facile synthesis and self-assembly of diazafluorenone-based p-n (donor-acceptor) organic semiconductors
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A mild and effective method to prepare 2,7-dibromo-4,5-diazafluoren-9-one (3) has been described involving tandem oxidation and rearrangement reactions. Diazafluorenone-based donor-acceptor (p-n) molecules via stille coupling reactions exhibit solvent-dep
- Li, Wei-Jie,Wu, Hai-Mei,Li, Yi-Bao,Hu, Chao-Peng,Yi, Ming-Dong,Xie, Ling-Hai,Chen, Lin,Zhao, Jian-Feng,Zhao, Xiang-Hua,Shi, Nai-En,Qian, Yan,Wang, Chen,Wei, Wei,Huang, Wei
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- D-π-A dye sensitizers made of polymeric metal complexes containing 1,10-phenanthroline and alkylfluorene or alkoxybenzene: Synthesis, characterization and photovoltaic performance for dye-sensitized solar cells
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Four polymeric metal complexes (P1-P4 based on 1,10-phenanthroline metal complexes and alkylfluorene or alkoxybenzene were synthesized by the Heck coupling reaction and were developed for dye-sensitized solar cell applications. The target dyes use alkoxyb
- Yu, Xiaoguang,Jin, Xueliang,Tang, Guipeng,Zhou, Jun,Zhang, Wei,Peng, Dahai,Hu, Jiaomei,Zhong, Chaofan
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- Synthesis and luminescent properties of novel silicon-based electroluminescent copolymers with ruthenium(II)-chelated complexes
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A new class of silicon-based alternating copolymers having Ruthenium(II)-chelated complexes was synthesized to use as electroluminescent materials by Heck reaction between organosilicon divinyl monomers and Ru(II)-chelated monomers. The incorporation of o
- Baek, Nam Seob,Kim, Hwan Kyu,Hwang, Gil Tae,Kim, Byeang Hyean
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- Novel donor-acceptor type thiophene pyridine conjugates: Synthesis and ion recognition features
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In order to reveal the effect of the donor units on the structure-property relationship, three novel directly linked donor-acceptor type systems, 1-3, which are based on thiophene and pyridine conjugates, are designed, synthesized and characterized by spe
- Algi, Fatih
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- Simple One-Step Synthesis of 3-Bromo- and 3,8-Dibromo-1,10-Phenanthroline: Fundamental Building Blocks in the Design of Metal Chelates
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Commercially available 1,10-phenanthroline monohydrochloride monohydrate (1) reacts with bromine to give 3-bromo-1,10-phenanthroline (2) and 3,8-dibromo-1,10-phenanthroline (3) as major products in a one step reaction.
- Tzalis, Dimitrios,Tor, Yitzhak,Failla, Salvatorre,Siegel, Jay S.
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- A highly efficient red-emitting ruthenium complex with 3,5-difluorophenyl substituents
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Five 3,5-difluorophenyl-substituted ruthenium complexes [Ru(bpy)2(dfpbpy)(ClO4)2] (Ru-Fbpy-bpy; bpy=bipyridine, dfpbpy=5,5′-di(3,5-difluorophenyl)-2,2′-bipyridine), [Ru(dpp)2(dfpbpy)(ClO4)2] (Ru-Fbpy-dpp; dpp=4,7-diphenyl-1,10-phenanthroline), [Ru(dpp)2(dfpphen)(ClO4)2] (Ru-Fphen-dpp; dfpphen=5,5′-di(3,5-difluorophenyl)-1,10-phenanthroline), [Ru(dpp)2(4,7-dfpphen)(ClO4)2] (Ru-Fdpp-dpp; 4,7-dfpphen=4,7-di(3,5-difluorophenyl)-1,10-phenanthroline), and [Ru(4,7-dfpphen)3(AsF6)2] (Ru-Fdpp) were synthesized, and their photophysical, electrochemical, and electroluminescent properties were studied systematically. The introduction of the electron-withdrawing group 3,5-difluorophenyl leads to a redshift of the emission of the ruthenium complexes. In addition, the 3,5-difluorophenyl substituent extends the π conjugation of the ligand, and thus facilitates the metal-to-ligand charge-transfer process of the complexes. All the complexes display orange-red phosphorescent emissions centered at 638, 638, 624, 614, and 605 nm, respectively. Density functional theory calculations show that the lowest unoccupied molecular orbital of Ru-Fbpy-dpp, Ru-Fphen-dpp, and Ru-Fdpp-dpp are all distributed on the 3,5-difluorophenyl-substituted ligand. By using these complexes as emitters, highly luminescent single-layer devices are obtained. The optimized device based on Ru-Fdpp exhibits the highest luminous efficiency and power efficiency of 4.19 cd A-1 and 1.46 lm W-1, respectively. Bright ideas: Five 3,5-difluorophenyl-substituted ruthenium complexes have been synthesized and characterized. The photoluminescent efficiencies of the complexes improved after introduction of an electron-withdrawing substituent (see scheme). The complexes are suitable as dopant light-emitting materials for organic light-emitting diodes.
- Zhu, Yingying,Fei, Teng,Ma, Yuguang
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- Preparation and properties of ?-conjugated poly(1,10-phenanthroline-3,8-diyl)
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Poly(1,10-phenanthroline-3,8-diyl) has been synthesized by dehalogenation polycondensation of 3,8-dibromo-1,10-phenanthroline with a zerovalent nickel complex.The polymer has molecular weihgt of 6800 and is electrochemically reduced at Epa=2.24
- Saitoh, Yutaka,Yamamoto, Takakazu
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- Synthesis of water soluble PEG-functionalized iridium complex via click chemistry and application for cellular bioimaging
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A water soluble iridium (III) complex was prepared via click chemistry. It shows the bright red phosphorescence centered at 625 nm with a quantum yield of ～ 1.4% in the phosphate buffered saline (PBS) solution. Furthermore, it has low cytotoxicity, good m
- Yang, Hong,Li, Liutao,Wan, Liqiang,Zhou, Zhiguo,Yang, Shiping
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- Synthesis and photophysical properties of 3,8-disubstituted 1,10-phenanthrolines and their ruthenium (II) complexes
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The palladium-catalysed cross-coupling reaction between 3,8-dibromo-1,10-phenanthroline with phenylacetylene or 3, 5-bis (trifluoromethyl) phenylboronic acid gives good yields of the 3, 8-disubstituted products. These 1,10-phenanthroline derivatives are used for the formation of novel ruthenium complexes of the type [(tbbpy)2Ru(phenR 2)]2+ [where tbbpy = 4, 4′-di-tert-butyl-2,2′- bipyridine, phen = 1, 10-phenanthroline, R represents the substituents at the 3, 8 positions with bromine, phenylacetylene or 3, 5-bis (trifluoromethyl)phenyl]. All compounds are completely characterised by NMR and UV/Vis spectroscopy, MS, electrochemical measurements and Raman and resonance Raman spectroscopy. The photophysical properties indicate a strong influence of the substitution of the phenanthroline ligand on the absorption, emission and Raman properties. With resonance Raman spectroscopy the localisation of the singlet metal-to-ligand charge-transfer (1MLCT) excited state is determined. The solid-state structures of 3, 8-dibromo-1, 10-phenanthroline (phenBr2) and the corresponding ruthenium complex [(tbbpy)2Ru(phenBr2)] 2+ and a structural motif of f(tbbpy)2- Ru[phen-3,8-bis[3, 5-bis (trifluoromethyl)phenyl]}]2+ are also reported.
- Karnahl, Michael,Krieck, Sven,Goerls, Helmar,Tschierlei, Stefanie,Schmitt, Michael,Popp, Juergen,Chartrand, Daniel,Hanan, Garry S.,Groarke, Robert,Vos, Johannes G.,Rau, Sven
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- Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
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Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Page/Page column 39; 90
(2020/06/03)
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- Iridium-europium heterogeneous polynuclear metal complex and its preparation method and use
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The invention belongs to the field of organic electroluminescence and relates to an iridium-europium heterogeneous polynuclear metal complex and its preparation method and use. A cyclometalated iridium complex-containing neutral ligand as a second ligand,
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Paragraph 0073; 0083; 0084
(2016/10/08)
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- Construction and luminescence property of a highly ordered 2D self-assembled amphiphilic bidentate organoplatinum(II) complex
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Rod-coil shaped amphiphilic bidentate dichloro(phenanthroline)platinum(ii) complexes, 1-Pt and 2-Pt, which possess different hydrophilic lateral chains on one side of an identical aromatic rod core, are synthesized. 1-Pt first forms dimers then arranges into well-defined two-dimensional (2D) films consisting of highly ordered molecular arrays both from methanol and on substrate. 2-Pt, as a building-block, yields micrometer-sized rigid 2D sheets without formation of an initial dimer. Red luminescence of the film is induced by self-assembly of nonemissive 1-Pt molecules, whereas sheets based on nonemissive 2-Pt gives weak yellow emission. These results indicate that the coil-rod ratio plays an important role in the structure and optical properties of these self-assemblies. Moreover, the film on the substrate at the macroscopic scale, exhibits multi-stimuli responsiveness, which predicts its application in smart chemosensing devices and probes.
- Xiang, Yunjie,Li, Wenjing,Fang, Yuxi,Zhang, Dengqing,Li, Xianying,Jin, Wusong
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p. 27360 - 27369
(2016/03/30)
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- Organic compound and Light emitting diode and Organic light emitting diode display device using the same
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Provided in the present invention is an organic compound having excellent hole injecting properties and electric-charge producing properties, and having a structure in which an electron withdrawing group is substituted for a phenanthroline core.COPYR
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Paragraph 0094-0097
(2016/10/10)
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- Bipyridine- and phenanthroline-based metal-organic frameworks for highly efficient and tandem catalytic organic transformations via directed C-H activation
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We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal-organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C-H borylation of arenes using B2pin2. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C-H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.
- Manna, Kuntal,Zhang, Teng,Greene, Francis X.,Lin, Wenbin
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supporting information
p. 2665 - 2673
(2015/03/04)
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- Iridium-Catalyzed Borylation of Primary Benzylic C-H Bonds without a Directing Group: Scope, Mechanism, and Origins of Selectivity
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Primary benzylic boronate esters are useful intermediates in organic synthesis, but these reagents cannot be prepared by hydroboration. The benzylic C-H borylation of methylarenes would be a method to form these products, but such reactions without neat methylarene or a directing group are unknown. We report an approach to divert the borylation of methylarenes from aromatic positions to benzylic positions with a silylborane as reagent and a new iridium catalyst containing an electron-deficient phenanthroline as ligand. This system forms benzylic boronate esters selectively over the corresponding aryl boronate esters. An Ir diboryl monosilyl complex ligated by the phenanthroline was isolated and determined to be the resting state of the catalyst. Mechanistic studies show that this complex is kinetically competent to be an intermediate in the catalytic process. Kinetic studies of benzylic and aryl C-H borylation catalyzed by various Ir complexes show that the rate of aryl C-H borylation decreases with decreasing electron density at the metal center of the Ir catalyst, but that the rate of benzylic C-H borylation is less sensitive to the degree of electron density at the metal center of the Ir catalyst. Kinetic and computational studies suggest that the two borylation reactions respond differently to the degree of electron density at the metal center because they occur with different turnover-limiting steps. The turnover-limiting step in the borylation of aryl C-H bonds is known to be C-H oxidative addition, but the turnover-limiting step of the borylation of benzylic C-H bonds appears to be an isomerization prior to C-B reductive elimination.
- Larsen, Matthew A.,Wilson, Conner V.,Hartwig, John F.
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supporting information
p. 8633 - 8643
(2015/07/15)
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- Synthesis and characterization of novel rhenium (I) complexes with large Stokes shift for applications in organic electroluminescent devices
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Two novel tricarbonyl rhenium(I) (Re(I)) complexes with versatile building block (1,10-phenanthroline), i.e., Re-PPhen and Re-FPPhen (PPhen, 3,8-diphenyl-1,10-phenanthroline; FPPhen, 3,8-bis(4-fluorophenyl)-1,10- phenanthroline), were designed, synthesize
- Li, Xiao,Zhang, Dongyu,Lu, Gonghao,Xiao, Guoyong,Chi, Haijun,Dong, Yan,Zhang, Zhiqiang,Hu, Zhizhi
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experimental part
p. 1 - 7
(2012/08/13)
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- Synthesis and properties of 3,8-bis[4-(9H-carbazol-9-yl)phenyl]-1,10- phenanthroline for phosphorescent OLEDs
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A novel bipolar molecule, 3,8-bis[4-(9H-carbazol-9-yl)-phenyl]-1,10- phenanthroline (CZPT) was synthesized and employed as the host in phosphorescent organic light-emitting devices (OLEDs). A maximum luminance of 7000 cd/m 2 was achieved using fac-tris(2-phenylpyridine)iridium (Ir(ppy) 3) as the emitting material. Copyright
- Ge, Ziyi,Hayakawa, Teruaki,Ando, Shinji,Ueda, Mitsuru,Akiike, Toshiyuki,Miyamoto, Hidetoshi,Kajita, Toru,Kakimoto, Masa-aki
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p. 262 - 263
(2008/09/20)
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- Synthesis of ladder polyaromatics as new molecular device candidates
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In order to investigate one of the proposed molecular electronics switching mechanisms, we synthesized several molecules whose cores are unable to undergo conformational rotation. Preparation of these molecules, all of which are terminated with the thioac
- Ciszek, Jacob W.,Tour, James M.
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p. 2801 - 2803
(2007/10/03)
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- Liquid-crystalline phenanthrolines
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The synthesis and mesomorphism of the first liquid-crystalline phenanthrolines are reported.
- Bousquet,Bruce
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p. 1769 - 1771
(2007/10/03)
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- Selective and efficient synthesis of di-, tri- and tetrasubstituted 1,10-phenanthrolines
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A general synthetic procedure for the preparation of multisubstituted phenanthrolines is presented. Bromination of 1,10-phenanthroline at the 3 and 8 positions, followed by Suzuki coupling reaction subsequent methylation afford the di-, tri and tetra- substituted phenanthrolines in good yields. These phenanthroline derivatives are useful building blocks in the construction of highly sophisticated molecular architectures.
- Dietrich-Buchecker, Christiane,Jimenez, M. Consuelo,Sauvage, Jean-Pierre
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p. 3395 - 3396
(2007/10/03)
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