- Rapid self-healing and anion selectivity in metallosupramolecular gels assisted by fluorine-fluorine interactions
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Simple ML2 [M = Fe(II), Co(II), Ni(II)] complexes obtained from a perfluoroalkylamide derivative of 4-aminophenyl-2,2′,6,2′-terpyridine spontaneously, yet anion selectively, self-assemble into gels, which manifest an unprecedented rapid gel strength recovery, viz. self-healing, and thermal rearrangement in aqueous dimethyl sulfoxide. The key factor for gelation and rheological properties emerges from the fluorine-fluorine interactions between the perfluorinated chains, as the corresponding hydrocarbon derivative did not form metallogels. The perfluoro-terpyridine ligand alone formed single crystals, while its Fe(II), Co(II) or Ni(II) complexes underwent rapid gelation leading to highly entangled fibrillar networks visualized by electron microscopy. The thermodynamic parameters of gelation based on variable temperature NMR 1H and 19F resonances showed that gelation was enthalpically favourable and entropically disfavourable. The step strain rheological experiments revealed that the gels undergo rapid self-healing and the morphological features, thermal stability and mechanical properties were found to depend on the nature of the metal ion.
- Arnedo-Sánchez, Leticia,Nonappa,Bhowmik, Sandip,Hietala, Sami,Puttreddy, Rakesh,Lahtinen, Manu,De Cola, Luisa,Rissanen, Kari
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- A luminescent ph-responsive ternary europium(Iii) complex of β-diketonates and terpyridine derivatives as sensitizing antennae – photophysical aspects, anion sensing, and biological interactions
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The highly luminescent stable Eu3+ complex [Eu(tta)3(naptpy)] [1, tta = 2-thenoyltrifluoroacetone, naptpy = 2-{4-[(2,2′:6′,2′′-terpyridin)-4′-yl]phenyl}-6-bromo-1H benzo-[de]isoquinoline-1,3(2H)-dione] was designed as a pH-responsive anion-sens
- Gupta, Kritika,Patra, Ashis K.
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- Photophysical properties of osmium(II) complexes with the novel 4'-p-phenylterpyridine-triarylpyridinium ligand
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A new family of electron acceptor ligands complexed with osmium(II) and associated with appropriate electron donor subunits within heteroleptic compounds, results in multicomponent assemblies of potential interest for both synthetic chemistry and supramol
- Laine, Philippe,Amouyal, Edmond
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- Transition metal ion induced hydrogelation by amino-terpyridine ligands
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Hydrogelation behavior of two amino-terpyridine ligands in the presence of divalent metal ions in water was studied in detail. The effect of ligand structure and different counter anions on the gel morphologies was also explored. This journal is
- Bhowmik, Sandip,Ghosh, Biswa Nath,Rissanen, Kari
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Read Online
- Fluorescent supramolecular polymers: Metal directed self-assembly of perylene bisimide building blocks
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Complezation properties of 2,2′:6′,2″-terpyridine (tpy) have been studied with, a series of first row transition metal ions by UV-vis, 1H NMR, and isothermal titration calorimetry, and AH values for the tpy complexation processes have been dete
- Dobrawa, Rainer,Lysetska, Marina,Ballester, Pablo,Gruene, Matthias,Wuerthner, Frank
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- Palladium supported terpyridine modified magnetic nanoparticles as an efficient catalyst for carbon-carbon bond formation
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In this paper, a novel catalyst is designed, synthesized and characterized based on the functionalization of magnetic iron oxide nanoparticles by terpyridine as a ligand for the immobilization of palladium. The catalyst is fully characterized by several c
- Baloutaki, Bahram Ahmadi,Sayahi, Mohammad Hosein,Nikpassand, Mohammad,Kefayati, Hassan
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- Luminescent lanthanide(III) complexes of DTPA-bis(amido-phenyl-terpyridine) for bioimaging and phototherapeutic applications
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We report here a series of coordinatively-saturated and thermodynamically stable luminescent [Ln(dtntp)(H2O)] [Ln(III) = Eu (1), Tb (2), Gd (3), Sm (4) and Dy (5)] complexes using an aminophenyl-terpyridine appended-DTPA (dtntp) chelating ligand as cell imaging and photocytotoxic agents. The N,N″-bisamide derivative of H5DTPA named as dtntp is based on 4′-(4-aminophenyl)-2,2′:6′,2″-terpyridine conjugated to diethylenetriamine-N,N′,N″-pentaacetic acid. The structure, physicochemical properties, detailed photophysical aspects, interaction with DNA and serum proteins, and photocytotoxicity were studied. The intrinsic luminescence of Eu(III) and Tb(III) complexes due to f → f transitions used to evaluate their cellular uptake and distribution in cancer cells. The solid-state structure of [Eu(dtntp)(DMF)] (1·DMF) shows a discrete mononuclear molecule with nine-coordinated {EuN3O6} distorted tricapped-trigonal prism (TTP) coordination geometry around the Eu(III). The {EuN3O6} core results from three nitrogen atoms and three carboxylate oxygen atoms, and two carbonyl oxygen atoms of the amide groups of dtntp ligand. The ninth coordination site is occupied by an oxygen atom of DMF as a solvent from crystallization. The designed probes have two aromatic pendant phenyl-terpyridine (Ph-tpy) moieties as photo-sensitizing antennae to impart the desirable optical properties for cellular imaging and photocytotoxicity. The photostability, coordinative saturation, and energetically rightly poised triplet states of dtntp ligand allow the efficient energy transfer (ET) from Ph-tpy to the emissive excited states of the Eu(III)/Tb(III), makes them luminescent cellular imaging probes. The Ln(III) complexes show significant binding tendency to DNA (K ~ 104 M?1), and serum proteins (BSA and HSA) (K ~ 105 M?1). The luminescent Eu(III) (1) and Tb(III) (2) complexes were utilized for cellular internalization and cytotoxicity studies due to their optimal photophysical properties. The cellular uptake studies using fluorescence imaging displayed intracellular (cytosolic and nuclear) localization in cancer cells. The complexes 1 and 2 displayed significant photocytotoxicity in HeLa cells. These results offer a modular design strategy with further scope to utilize appended N,N,N-donor tpy moiety for developing light-responsive luminescent Ln(III) bioprobes for theranostic applications.
- Dasari, Srikanth,Singh, Swati,Abbas, Zafar,Sivakumar, Sri,Patra, Ashis K.
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- Aggregation induced emission (AIE) active 4-amino-1,8-naphthalimide-Tr?ger's base for the selective sensing of chemical explosives in competitive aqueous media
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The 4-amino-1,8-naphthalimide-Tr?ger's base fluorophore, TBNap-TPy, adorned with phenyl-terpyridine moiety was synthesised and assessed for its aggregation-induced emission (AIE) behaviour. TBNap-TPy was further employed as a fluorescent sensor for the di
- Delente, Jason M.,Gunnlaugsson, Thorfinnur,Kotova, Oxana,Shanmugaraju, Sankarasekaran,Umadevi, Deivasigamani,Watson, Graeme W.
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p. 2562 - 2565
(2020/03/10)
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- A novel bis(terpyridine) with π?conjugated phenyl viologen and its metallo- supramolecular polymers: Synthesis and electrochromism
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A novel phenylene viologen functionalized bis(terpyridine) is synthesized and characterized with 1HNMR and Maldi-tof-MS. This rod-like and π-conjugated molecule, 1,1'-[4'-(4-phenyl)-2,2:6′,2″- terpyridine-4,4′-bipyridine-1,1′-diium dichloride (
- Qian, Yuchen,Wang, Yuechuan,Yang, Han
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- Self-assembly and photo-responsive behavior of bis-terpyridyl Eu3+-complex L1
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In the present paper, a bis-terpyridyl Eu3+ complex (bis-terpyridyl Eu3+-complex L1) was synthesized through the coordination between Eu3+ and a compound L1 with an azobenzene-functionalized chain between the two terpyridi
- Dong, Chuan,Yuan, Jin,Hoffmann, Heinz,Hao, Jingcheng
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p. 19355 - 19364
(2019/12/24)
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- 2-(2′-Hydroxyphenyl)-benzothiazole (HBT)-terpyridine conjugate: A highly specific ICT based fluorescent probe for Zn2+ ions and its application in confocal cell imaging
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A new fluorescent sensor based on benzothiazole-terpyridine conjugate is reported. It functions as a fluorescent sensor that is highly selective for the Zn2+ ions via internal charge transfer (ICT) mechanism in DMSO: H2O medium. The
- Sahana, Sunanda,Mishra, Gargi,Sivakumar, Sri,Bharadwaj, Parimal K.
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p. 231 - 239
(2017/11/03)
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- Synthesis of heteroleptic terpyridyl complexes of Fe(II) and Ru(II): Optical and electrochemical studies
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We report the synthesis and characterization of heteroleptic terpyridyl complexes of d6 transition metal ions with Fe2+ and Ru2+ (1-3). Furthermore, we study the effect of substitution of either an electron donating group (-NH2) or electron withdrawing group (-NO2) at the 4′-position in the ligands by means of UV-vis, cyclic voltammetry, and differential pulse voltammetry measurements. The experimentally observed photophysical characteristics of the transition-metal based terpyridyl complexes are explained and supported by detailed quantum chemical calculations.
- Mondal, Prakash Chandra,Manna, Arun Kumar
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p. 5775 - 5781
(2016/07/16)
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- Perylene-based, bis(terpyridine)-ru(ii) complexes: synthesis, electrochemical and photovoltaic properties
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Perylene-based, terpyridine-Ru(II) complexes are synthesized and their electrochemical and photoelectrochemical properties are studied; their fabrication into dye-sensitized solar cells are described (DSSCs) and their resultant photovoltaic properties are
- El-Batal, Hany,Rocha, Juan Manrquez,Mndez, Perla F.,Godnez, Luis A.,Guo, Kai,Li, Xiaopeng,Lu, Xiaocun,Wesdemiotis, Chrys,Moorefield, Charles N.,Newkome, George R.
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p. 502 - 514
(2015/03/04)
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- Photoelectrochemical oxidation of a turn-on fluorescent probe mediated by a surface MnII catalyst covalently attached to TiO2 nanoparticles
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A manganese complex covalently attached to a TiO2 electrode via a light-absorbing organic linker (L) was used in the photooxidation of 20,70-dihydrodichlorofluorescein (H2DCF). Significant and sustained photocurrent was observed upon
- Durrell, Alec C.,Li, Gonghu,Koepf, Matthieu,Young, Karin J.,Negre, Christian F.A.,Allen, Laura J.,McNamara, William R.,Song, Hee-Eun,Batista, Victor S.,Crabtree, Robert H.,Brudvig, Gary W.
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- Optimising the synthesis, polymer membrane encapsulation and photoreduction performance of Ru(II)- and Ir(III)-bis(terpyridine) cytochrome c bioconjugates
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Ruthenium(ii) and iridium(iii) bis(terpyridine) complexes were prepared with maleimide functionalities in order to site-specifically modify yeast iso-1 cytochrome c possessing a single cysteine residue available for modification (CYS102). Single X-ray crystal structures were solved for aniline and maleimide Ru(ii) 3 and Ru(ii) 4, respectively, providing detailed structural detail of the complexes. Light-activated bioconjugates prepared from Ru(ii) 4 in the presence of tris(2-carboxyethyl)-phosphine (TCEP) significantly improved yields from 6% to 27%. Photoinduced electron transfer studies of Ru(ii)-cyt c in bulk solution and polymer membrane encapsulated specimens were performed using EDTA as a sacrificial electron donor. It was found that membrane encapsulation of Ru(ii)-cyt c in PS140-b-PAA48 resulted in a quantum efficiency of 1.1 ± 0.3 × 10-3, which was a two-fold increase relative to the bulk. Moreover, Ir(iii)-cyt c bioconjugates showed a quantum efficiency of 3.8 ± 1.9 × 10-1, equivalent to a ~640-fold increase relative to bulk Ru(ii)-cyt c.
- Hvasanov, David,Mason, Alexander F.,Goldstein, Daniel C.,Bhadbhade, Mohan,Thordarson, Pall
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p. 4602 - 4612
(2013/07/26)
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- Facile synthesis and photochromic properties of diarylethene-containing terpyridine and its transition metal (Zn2+/Co2+/Ru 2+) complexes
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Several transition metal complexes based on 2,3-bis(2,4,5-trimethyl-3- thienyl)maleic anhydride (DTE) bearing terpyridine (TPY) have been designed and synthesized. Furthermore, the photochromism of the free ligand and the influence of transition metal moi
- Zhang, Xiao-Chun,Huo, Zhi-Ming,Wang, Ting-Ting,Zeng, He-Ping
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p. 754 - 759
(2012/10/30)
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- Switchable supramolecular polymers from the self-assembly of a small monomer with two orthogonal binding interactions
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The low molecular weight heteroditopic monomer 1 forms supramolecular polymers in polar solution as shown, for example, by infrared laser-based dynamic light scattering (DLS), small-angle neutron scattering (SANS), electron microscopy (TEM, cryo-TEM), and
- Groeger, Gerd,Meyer-Zaika, Wolfgang,Boettcher, Christoph,Groehn, Franziska,Ruthard, Christian,Schmuck, Carsten
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supporting information; experimental part
p. 8961 - 8971
(2011/08/04)
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- Surface bottom-up fabrication of porphyrin-terminated metal complex molecular wires with photo-electron conversion properties on ITO
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We fabricated photoelectron conversion system with porphyrin-terminated "molecular wires" on an ITO surface synthesized using stepwise metal-terpyridine complexation reactions. The efficiency and the electrode potential singniflcantly depended on the meta
- Miyachi, Manko,Ohta, Makiko,Nakai, Misaki,Kubota, Yoshihiro,Yamanoi, Yoshinori,Yonezawa, Tetsu,Nishihara, Hiroshi
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p. 404 - 405
(2008/09/20)
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- High turnover remote catalytic oxygenation of alkyl groups: How steric exclusion of unbound substrate contributes to high molecular recognition selectivity
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H-bonding mediated molecular recognition between substrate and ligand -COOH groups orients the substrate so that remote, catalyzed oxygenation of an alkyl C-H bond by a Mn-oxo active site can occur with very high (>98%) regio- and stereoselectivity. This paper identifies steric exclusion - exclusion of non H-bonded substrate molecules from the active site - as one requirement for high selectivity, along with the entropic advantage of intramolecularity. If unbound substrate molecules were able to reach the active site, they would react unselectively, degrading the observed selectivity. Both of the faces of the catalyst are blocked by two ligand molecules each with a -COOH group. The acid p-tBuC6H4COOH binds to the ligand -COOH recognition site but is not oxidized and merely blocks approach of the substrate therefore acting as an effective inhibitor for ibuprofen oxidation in both free acid and ibuprofen ester form. Dixon plots show that inhibition is competitive for the free acid ibuprofen substrate, no doubt because this substrate can compete with the inhibitor for binding to the recognition site. In contrast, inhibition is uncompetitive for the ibuprofen-ester substrate, consistent with this ester substrate no longer being able to bind to the recognition site. Inhibition can be reversed with MeCOOH, an acid that can competitively bind to the recognition site but, being sterically small, no longer blocks access to the active site.
- Das, Siddhartha,Brudvig, Gary W.,Crabtree, Robert H.
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p. 1628 - 1637
(2008/09/18)
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- Photoinduced reduction of catalytically and biologically active Ru(II)bisterpyridine-cytochrome c bioconjugates
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Ruthenium(II)bisterpyridine chromophores were covalently linked to iso-1 cytochrome c from yeast to create light-activated donor-acceptor bioconjugates. The Royal Society of Chemistry.
- Peterson, Joshua R.,Smith, Trevor A.,Thordarson, Pall
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p. 1899 - 1901
(2008/02/08)
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- A new class of functionalized terpyridyl ligands as building blocks for photosensitized supramolecular architectures. Synthesis, structural, and electronic characterizations
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A new class of triarylpyridinio-derivatized [4′-(p- phenyl)n]terpyridyl ligands, R12R2TP+-(p)ntpy, was designed as a novel category of electron-acceptor (A)-substituted proto-photosensitizi
- Laine, Philippe,Bedioui, Fethi,Ochsenbein, Philippe,Marvaud, Valerie,Bonin, Michel,Amouyal, Edmond
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p. 1364 - 1377
(2007/10/03)
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- Phenyl-substituted 2,2′:6′,2″-terpyridine as a new series of fluorescent compounds - Their photophysical properties and fluorescence tuning
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Several phenyl-substituted 2,2′:6′,2″-terpyridines (tpy) were synthesized and it was found that 4′-phenyl tpy (ptp, 3) exhibited the most effective fluorescence, whose quantum yield was up to 0.64 in cyclohexane. For further study on tuning the fluorescence properties of ptp, different substituents were introduced into the p-position of the phenyl group. While Br- 10, Cl- 11, and CH3-ptp 12 showed their absorption and fluorescence in the same region as 3, those of NH2- 14 and Me2N-ptp 15 were observed at much longer wavelengths. In addition, fluorescence maxima of 14 and 15 showed large (> 130 nm) solvent dependence. The difference between ground and excited state dipole moment (Δμ) for 15 was estimated to be 15.2 D by the Lippert-Mataga equation, indicating the intramolecular charge transfer (ICT) process. Semi-empirical MO calculation (MOPAC/AM1) demonstrated that the HOMO-1, HOMO and LUMO of 3, 10-12 were mainly localized on the phenyl (πph), tpy (πtpy) and tpy (π*tpy) part, respectively, indicating that the lowest energy absorption band of 3, 10-12 was the local excitation (πtpy-π*tpy). In the case of 14 and 15, which have an electron-donating substituent, πph instead of πtpy became the HOMO. Thus, the lowest energy absorption of 14 and 15 was an ICT transition (πph-π*tpy), and a large red shift of the fluorescence occurred. In these compounds, the energy level of πph is controlled without affecting that of πtpy and π*tpy, suggesting a novel approach for tuning the color of fluorescence.
- Mutai, Toshiki,Cheon, Jin-Dong,Arita, Shinpei,Araki, Koji
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p. 1045 - 1050
(2007/10/03)
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- Synthesis and physical properties of a π-conjugated ruthenium(II) dinuclear complex involving an azobenzene-bridged bis(terpyridine) ligand
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A novel π-conjugated Ru(II) dinuclear complex containing a new azobenzene-bridged bis(terpyridine) ligand was synthesized and its photochemical and electrochemical properties were investigated. The ligand underwent reversible trans-cis photoisomerization,
- Yutaka, Tomona,Kurihara, Masato,Nishihara, Hiroshi
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p. 511/193 - 516/198
(2007/10/03)
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- Bis[4′-(4-anilino)-2,2′:6′,2″-terpyridine] transition-metal complexes: Electrochemically active monomers with a range of magnetic and optical properties for assembly of metallo oligomers and macromolecules
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The new ligand 4′-(4-anilino)-2,2′:6′,2″-terpyridine (L1) and a range of its transition-metal complexes have been prepared. The crystal and molecular structures of L1 and [CuL12[PF6]2 have been determined. Model reactions show that L1 and its transition-metal complexes can be functionalised with suitable organic reagents: reactions with aromatic dianhydrides give imide derivatives, reactions with acid chlorides afford amide derivatives and benzoquinone reacts with L1 to give a quinonylanilinoterpyridine ligand, complexes of which are described, but not with the complexes of L1. The use of L1 and its complexes in building up multicomponent architectures has been tested. Metallo-dimers and co-ordination polymers linked by new binucleating bis(terpyridyl) ligands have been prepared by two routes: (a) first coupling two L1 with difunctional organic reagents and then treating the new binucleating ligands with a metal source, or (b) preforming monomeric complexes of L1 and treating these with the same difunctional organic reagents. Analytical, spectroscopic and electrochemical data are given for all complexes; the chromophoric, magnetic and electrochemical properties of the complexes vary with transition metal and terpyridyl ligand substituent.
- Storrier, Gregory D.,Colbran, Stephen B.,Craig, Donald C.
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p. 3011 - 3028
(2007/10/03)
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- Transition-metal complexes of 4′(4-anilino)-2,2′:6′,2″-terpyridine (and derivatives): Versatile building blocks for construction of metallooligomers and macromolecules
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Transition-metal complexes of 4′(4-anilino)-2,2′:6′,2″-terpyridine have been prepared and used to construct co-ordination dimers and polymers linked by new binucleating terpyridine ligands. Copyright 1996 by the Royal Society of Chemistry.
- Storrier, Gregory D.,Colbran, Stephen B.
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p. 2185 - 2186
(2007/10/03)
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