- Synthesis and Co-ordination Behaviour of 6',6''-Bis(2-pyridyl)-2,2':4,4'':2'',2'''-quaterpyridine; 'Back-to-back' 2,2':6',2''-Terpyridine
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The oligopyridine 6',6''-bis(2-pyridyl)2,2':4,4'':2'',2'''-quaterpyridine (L) has been prepared.It may be regarded as a 'back-to-back' analogue of the well known 2,2':6',2''-terpyridine (terpy).Complexes with ruthenium(II) and palladium(II) have been characterised.The diruthenium(II) complex cation 4+ has been shown to exhibit no Ru-Ru interactions, and behaves as two non-interacting Ru(terpy)2 units.
- Constable, Edwin C.,Ward, Michael D.
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- The synthesis, photophysical properties and water oxidation studies of a series of novel photosensitizer–catalyst assemblies
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A novel series of bridging ligands and their RuIIphotosensitizer–catalyst dyads have been prepared and characterized by NMR and electronic absorption spectroscopy as well as cyclic voltammetry. The presence of asymmetry in the ligands facilitat
- Nair, Neelima V.,Zhou, Rongwei,Thummel, Randolph P.
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- Highly cytotoxic copper(II) terpyridine complexes as anticancer drug candidates
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Cancer is one of the deadliest diseases worldwide. Chemotherapy remains one of the frequently applied treatment modalities in the clinics. However, as the currently applied agents are associated with severe side effects, scientists are searching for novel chemotherapeutic drugs. Within the last decades, Cu(II) polypyridine complexes have received increasing attention as potential anticancer drug candidates. Herein, the biological activity of terminally functionalised mono- and bis-coordinated Cu(II)-2,2′:6′,2″-terpyridine complexes have been investigated. The bis-coordinated compounds were found to have a cytotoxic effect in the nanomolar range in human adenocarcinomic alveolar basal epithelial cells. Promisingly, the complexes were equally active in the corresponding cisplatin resistant cell line, indicating that they could potentially be useful for the treatment of drug resistant tumours.
- Karges, Johannes,Xiong, Kai,Blacque, Olivier,Chao, Hui,Gasser, Gilles
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- Reversible Self-Assembly of Water-Soluble Gold(I) Complexes
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The reaction of the gold polymers containing bipyridyl and terpyridyl units, [Au(C≡CC15H10N3)]n and [Au(C≡CC10H7N2)]n, with the water-soluble phosphines 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane gives rise to the formation of four gold(I) alkynyl complexes that self-assemble in water (H2O) and dimethyl sulfoxide (DMSO), through different intermolecular interactions, with an impact on the observed luminescence displayed by the supramolecular assemblies. A detailed analysis carried out by NMR studies performed in different DMSO/deuterated H2O mixtures indicates the presence of two different assembly modes in the aggregates: (i) chain assemblies, which are based mainly on aurophilic interactions, and (ii) stacked assemblies, which are based on Au···π and π···π interactions. These different supramolecular environments can also be detected by their intrinsic optical properties (differences in absorption and emission spectra) and are predicted by the changes in the relative binding energy from density functional theory calculations carried out in DMSO and H2O. Small-angle X-ray scattering (SAXS) experiments performed in the same mixture of solvents are in agreement with the formation of aggregates in all cases. The aromatic units chosen, bipyridine and terpyridine, allow the use of external stimuli to reversibly change the aggregation state of the supramolecular assemblies. Interaction with the Zn2+ cation is observed to disassemble the aggregates, while encapsulating agents competing for Zn2+ complexation revert the process to the aggregation stage, as verified by SAXS and NMR. The adaptive nature of the supramolecular assemblies to the metal-ion content is accompanied by significant changes in the absorption and emission spectra, signaling the aggregation state and also the content on Zn2+.
- Aguiló, Elisabet,Moro, Artur J.,Gavara, Raquel,Alfonso, Ignacio,Pérez, Yolanda,Zaccaria, Francesco,Guerra, Célia Fonseca,Malfois, Marc,Baucells, Clara,Ferrer, Montserrat,Lima, Jo?o Carlos,Rodríguez, Laura
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- New organic ligands of the terpyridine series: Modification of gold nanoparticles, preparation of coordination compounds with Cu(I), catalysis of oxidation reactions
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Organic ligands containing terpyridine and disulfide groupings linked between one another by a bonding -O(CH2) n- (n = 6, 12) fragment have been synthesized. Gold nanoparticles of mean size 1.8 nm modified with the indicated ligand were obtained by the method of Brust. By methods of electron spectroscopy and cyclic voltamperometry, the possibility of forming of coordinated compounds on the surface of gold nanoparticles modified by a terpyridine ligand, on interaction with Cu(MeCN)4ClO4 has been shown. The obtained nanoparticles catalyze the oxidation of 2,4-di-tert-butylphenol into 3,3',5,5'-tetra(tert-butyl)biphenyl-2,2'-diol.
- Majouga,Romashkina,Kashaev,Rahimov,Beloglazkina,Zyk
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- Multi-Readout Logic Gate for the Selective Detection of Metal Ions at the Parts Per Billion Level
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Optical sensors utilizing visual responses for the identification of metal ions require reliable molecular systems able to operate selectively in multicomponent solutions. Herein, we report a water-soluble terpyridyl-based ligand that demonstrates effective quantification of parts per billion to parts per million levels of Fe2+, Fe3+, Zn2+, and Ru3+. Whereas the Fe3+and Ru3+ions were found to bind to the ligand to form a monometallic complex, a 2:1 ligand/metal binding stoichiometry was found for the Zn2+and Fe2+complexes. The corresponding metal-binding events were directly translated into distinct colorimetric and spectroscopic logic outputs. Applying molecular logic (Boolean logic operations) to describe these binding events, selective discrimination between the ions was demonstrated.
- Laschuk, Nadia O.,Ebralidze, Iraklii I.,Spasyuk, Denis,Zenkina, Olena V.
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- Ruthenium(II) complex-induced dispersion of montmorillonite in a segmented main-chain liquid-crystalline polymer having side-chain terpyridine group
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An experiment was conducted in which the ruthenium (II) complex in a functional liquid-crystalline polymer exfoliated the pristine MMT aggregates through the Coulombic interactions between the positively charged ruthenium center and the negatively charged MMT surfaces. A segmented main-chain liquid crystalline polymer was synthesized having side-chain terpyridine group (PTBP) and ruthenium complex was prepared by mixing PTBP with a monocomplex which was formed between a terpyridine and ruthenium chloride. X-ray diffraction (XRD) experiments were conducted on a Rigaku Rotaflex rotating anode diffractometer with slit collimation to determine the degree of dispersion of MMT aggregates in the nanocomposites. The observation provided a new concept for molecular design to achieve a high degree of dispersion of the aggregates of natural clay in the polymer matrix without the need to treat the natural clay with surfactant.
- Huang, Wenyi,Han, Chang Dae
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- Two-Photon Absorption Properties in “Push-Pull” Ruthenium Nitrosyl Complexes with various Fluorenylterpyridine-Based Ligands
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Using the compound [RuII(FT)(bipy)(NO)](PF6)3 (FT is the electron-rich 4’-(2-fluorenyl)-2,2’:6’,2’’-terpyridine ligand and bipy is 2–2’bipyridine) as a reference, two new compounds are presented in which carbon-carbon double and triple bonds are inserted between the fluorenyl substituent and the terpyridine to provide an extended conjugation path. The electronic properties of the three complexes are compared experimentally by UV-visible spectroscopy and computationally by means of the density functional theory. All of them exhibit a capability for NO release under irradiation on their low-energy transition located in the 400–500 nm range, with a quantum yield around 0.01. Their two-photon absorption (TPA) cross sections are investigated by the Z-scan technique at λ=800 nm. While the reference compound exhibits a cross-section equal to 108 GM, the introduction of double and triple bonds leads to increased cross-sections equal to 131 GM and 150 GM, respectively. These values are discussed in reference to the two-level model in use for “push-pull” dipolar TPA chromophores.
- Bukhanko, Valerii,León-Rojas, Andrés Felipe,Lacroix, Pascal G.,Tassé, Marine,Ramos-Ortiz, Gabriel,Barba-Barba, Rodrigo M.,Farfán, Norberto,Santillan, Rosa,Malfant, Isabelle
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p. 1670 - 1684
(2021/05/03)
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- Supramolecular architectures self-assembled using long chain alkylated spin crossover cobalt(II) compounds
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Self-assembled hybrid supramolecular architectures formed between amphiphilic anions and long alkylated cationic cobalt(ii) complexes of type [Co(Cn-terpy)2](C12-Glu)2 (n = 15-20) have been synthesized and characterized by TEM, PXRD and magnetic susceptibility measurements. The hybrids display wire or rolled sheet supramolecular arrangements with odd and even alkyl chain dependence, with the cobalt(ii) centres exhibiting gradual spin-crossover behaviours.
- Akiyoshi, Ryohei,Kuroiwa, Keita,Alao Amolegbe, Saliu,Nakaya, Manabu,Ohtani, Ryo,Nakamura, Masaaki,Lindoy, Leonard F.,Hayami, Shinya
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p. 4685 - 4687
(2017/07/10)
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- Isolation and structure of a hydrogen-bonded 2,2':6',2'-terpyridin-4'-one acetic acid adduct
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Herein, we report the crystal structure of a key intermediate in the synthesis of 4'-substituted-terpyridines. Our findings confirm that the terpyridin-4'-one intermediate as generated from the condensation reaction of the corresponding triketone precursor with ammonium acetate is isolated as a hydrogen-bonded adduct with acetic acid, and not, as previously reported, as the acetate salt of a protonated pyridine nitrogen. This finding provides a rationale for the behaviour and structure of substituted terpyridin-4'-ones and pyridones in both the solid state and in solution. CSIRO 2014.
- Florio, Pas,Coghlan, Campbell J.,Lin, Chih-Pei,Saito, Kei,Campi, Eva M.,Jackson, W. Roy,Hearn, Milton T.W.
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p. 651 - 656
(2014/05/06)
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- Modular syntheses of star-shaped pyridine, bipyridine, and terpyridine derivatives by employing sonogashira reactions
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A simple and flexible synthesis for a series of star-shaped pyridine, bipyridine, and terpyridine derivatives is reported by using a modular approach that combines the use of a ligand, spacer, and core unit. A fairly efficient method to prepare 4′-nonafloxy-functionalized terpyridine derivatives is described. The building blocks that contain the functionalized pyridine, bipyridine, or terpyridine derivatives were linked to different C3-symmetrical core units. In most cases, Sonogashira reactions were employed in the crucial final steps of the synthesis. A star-shaped dodecafluorinated compound was also prepared in a straightforward fashion. A simple procedure for the preparation of partially silylated 1,3,5-triethynylbenzene derivatives is presented, which provides an approach to C2-symmetrical star-shaped compounds that have only one terpyridine and two terphenyl units as "dummy" ligands. The absorption and emission spectra of the fully conjugated C3-symmetrical pyridine derivatives were systematically investigated, and fairly large Stokes shifts were observed.
- Trawny, Daniel,Kunz, Valentin,Reissig, Hans-Ulrich
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p. 6295 - 6302
(2015/03/30)
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- Communication between components in metal-directed assemblies of oriented calix[6]arene-based pseudorotaxanes and rotaxanes
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Oriented calix[6]arene-based pseudorotaxanes and rotaxanes where the axial component bears a terpyridine ligand as a stopper positioned at the upper rim of the calixarene have been synthesized. The binding ability of the terpyridine unit present in the ax
- Arduini, Arturo,Bussolati, Rocco,Masseroni, Daniele,Royal, Guy,Secchi, Andrea
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p. 1033 - 1038
(2012/03/27)
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- Synthesis of new dendritic antenna-like polypyridine ligands
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An efficient synthesis of multidentate polypyridine ligands, 3,5-bis(2,2′-bipyridin-4-ylethynyl)benzoic acid and 3,5-bis(2,5-bis(2- pyridyl)-pyridin-4-ylethynyl)benzoic acid, with potential application in the production of ruthenium dyes for dye-sensitised solar cells was developed. Isolation of intermediate products and final compounds is simple and the yields are very high. The ligands obtained can be used in the synthesis of dendritic analogues of well known and very efficient N3 dye and "black dye".
- Zalas, Maciej,Gierczyk, Blazej,Ceglowski, Michal,Schroeder, Grzegorz
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p. 733 - 740
(2013/07/26)
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- A rigid metallohexameric macrocycle composed of endo- and exo-cyclic bisterpyridine-metal complexes
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Synthesis of terpyridine-based building blocks has allowed the self-assembly of a nanosized metallomacrocycle with precisely positioned, peripheral metal complexes. Construction of the precursors included the assembly of a heteroleptic bisterpyridine-Ru(ii) complex possessing a diiodoaryl moiety that was subsequently reacted with two equivalents of 4′-ethynyl-2, 2′:6′,2′′-terpyridine via a Pd(0)-catalyzed Sonagashira coupling, to generate the requisite monomer with two, 120°-juxtaposed metal coordination sites. Addition of one equivalent of Fe(ii) to one equivalent of the bisligand afforded the metallocycle with 12 metals [6 internal Fe(ii) ions and 6 external Ru(ii) ions] measuring ca. 7 nm in diameter.
- Li, Sinan,Moorefield, Charles N.,Shreiner, Carol D.,Wang, Pingshan,Sarkar, Rajarshi,Newkome, George R.
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p. 2130 - 2135
(2011/11/13)
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- Use of metal complex compounds as catalysts for oxidation using molecular oxygen or air
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Use, as a catalyst for oxidation reactions using molecular oxygen and/or air, of at least one metal complex compound of formula (1) wherein Me is manganese, titanium, iron, cobalt, nickel or copper, X is a coordinating or bridging radical, n and m are each independently of the other an integer having a value of from 1 to 8, p is an integer having a value of from 0 to 32, z is the charge of the metal complex, Y is a counter-ion, q=z/(charge of Y), and L is a ligand of formula (2) wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 are each independently of the others hydrogen; unsubstituted or substituted C1-C18alkyl or aryl; cyano; halogen; nitro; —COOR12 or —SO3R12 wherein R12 is in each case hydrogen, a cation or unsubstituted or substituted C1-C18alkyl or aryl; —SR13, —SO2R13 or —OR13 wherein R13 is in each case hydrogen or unsubstituted or substituted C1-C18alkyl or aryl; —NR14R15; —(C1-C6alkylene)-NR14R15; —N(+)R14R15R16; —(C1-C6alkylene)-N(+)R14R15R16; —N(R13)—(C1-C6alkylene)-NR14R15; —N[(C1-C6alkylene)-NR14R15]2; —N(R13)—(C1-C6alkylene)-N(+)R14R15R16; —N[(C1-C6alkylene)-N(+)R14R15R16]2; —N(R13)—N—R14R15 or —N(R13)N″R14R15R16, wherein R13 is as defined above and R14, R15 and R16 are each independently of the other(s) hydrogen or unsubstituted or substituted C1-C18alkyl or aryl, or R14 and R15, together with the nitrogen atom linking them, form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain further hetero atoms. [in-line-formulae][LnMemXp]zYq??(1) [/in-line-formulae]
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Page/Page column 14-15
(2010/02/15)
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- Amphiphilic Terpyridine Complexes of Ruthenium and Rhodium displaying Lyotropic Mesomorphism
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New 4'-alkyl-substituted 2,2':6',2''-terpyridine (4'R-terpy) compounds have been synthesised from 4'-methyl-2,2':6',2''-terpyridine and an appropriate 1-bromoalkane and complexed with ruthenium and rhodium to yield new bis(terpyridine) complexes (2+) (R = C19H39 or C31H63) and (3+) (R = C19H39) as chloride and hexafluorophosphate salts.These complexes are amphiphilic being structurally related to surfactant tris(bipyridine)ruthenium complexes.Both ruthenium and rhodium complexes with R = C19H39 and chloride counter ions show lyotropic mesomorphism in water, and the ruthenium complex with R = C31H63 shows mesophase formation in ethylene glycol.
- Holbrey, John D.,Tiddy, Gordon J. T.,Bruce, Duncan W.
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p. 1769 - 1774
(2007/10/02)
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