- Room temperature photoluminescence from [Pt(4′-CCR-tpy)Cl] + complexes
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The synthesis, photophysics, electronic structure, and electrochemical characterization of 4′-tert-butylacetylene-2,2′:6′,2″- terpyridineplatinum(ii) chloride (1), 4′-phenylacetylene-2,2′: 6′,2″-terpyridineplatinum(ii) chloride (2), and their Zn II/
- Muro, Maria L.,Castellano, Felix N.
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- Synthesis, characterization and preliminary investigation of the electro redox properties of anthracenyl-functionalized terpyridyl ligands
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We report the synthesis, characterization and preliminary investigation of the electro redox properties of soluble bromoterpyridine ligand precursors L1, L2 and L3 having one to three anthracenyl modules. The synthetic protocol is based on sequential palladium cross-coupling reactions between 9,10-dibromoanthracene and bromoterpyridine, 9-bromoanthracene-terpyridine or 9-bromo-dianthraceneterpyridine synthons. With increasing numbers of anthracene units on the terpyridine ligand, common absorption wavelengths at the near visible region and enhanced molar absorptivity coefficients were recorded. However, the luminescence intensity decreases with increasing length of π-conjugation relating to aggregation effects in the molecules. The cyclic voltammograms of L1 and L2 display good electro redox activity, being better than that of L3.
- Adeloye, Adewale O.,Ajibade, Peter A.
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- Solvent-free synthesis of bis(2,2′:6′,2″-terpyridin- 4′-yl)amine and its metal complexes
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The key compound bis(2,2′:6′,2″-terpyridin-4′-yl) amine was prepared in one step starting from 4′-amino-2,2′:6′, 2″-terpyridine and 4′-bromo-2,2′:6′,2″-terpyridine in quantitative yield. In addition, we have established an easy and efficient route for the
- Fallahpour, Reza-Ali
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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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supporting information
(2020/11/26)
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- Method for large-scale production of 4'-bromo-2,2': 6',2''-terpyridine
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The invention discloses a method for large-scale production of 4'-bromo-2,2': 6',2''-terpyridine. The method comprises the following steps: a) subjecting 4'-hydroxy-2,2': 6',2''-terpyridine to reacting with trifluoromethanesulfonic anhydride to prepare 2,2': 6',2'-terpyridine-4'-trifluoromethanesulfonate; and b) carrying out a reaction on the 2,2': 6',2'-terpyridine-4'-trifluoromethanesulfonate and hydrobromic acid to prepare 4'-bromo-2,2': 6',2''-terpyridine. Experiments show that the method is mild in reaction conditions, simple to operate, easy in purification treatment and high in yield, and the target product with HPLC purity as high as 99.4% can be obtained through simple recrystallization treatment; and particularly, the method is easy to realize production scale from kilogram level to hundred kilogram level, the whole production period is short, and production cost can be reduced by at least 40% compared with the prior art.
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Paragraph 0042-0050
(2021/10/20)
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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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supporting information
p. 1017 - 1028
(2018/02/14)
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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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- Terminal redox-site effect on the long-range electron conduction of Fe(tpy)2 oligomer wires on a gold electrode
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This article completes our comprehensive understanding of the electron transport properties of our original p-conjugated redox-active molecular wires comprising Fe bridged by p-phenylene linkers (tpy=2,2':6',2''-terpyridine). The Fe(tpy)2 oligomer wires comprise three types of tpy ligands: the anchor tpy ligand (A series) makes a junction between the wire and electrode, the bridging bis-tpy ligand (L series) connects the Fe(tpy)2 units, and the terminal tpy ligand (T series) possesses a redox site as a probe for the long-range electron transport ability. Taking advantage of the precise tunability of the composition of the Fe- (tpy)2 oligomer wires, thus far we investigated how A and L impacted on the electron-transport ability. The excellent long-range electron transport ability with ultrasmall attenuation constants (bd, 0.002 -1 as the minimum) depends on L significantly [Chem. Asian J. 2009, 4, 1361], whereas A is unrelated to the bd value, but influences the zero-distance electron-transfer rate constant, ket 0 [J. Am. Chem. Soc.2010, 132, 4524]. Herein we study the influence of terminal ligand Tx (x=1- 3). bd is independent of T, however, T3, with a cyclometallated Ru complex as the redox site, gives rise to a ket 0 value greater than T1 and T2 with ferrocene. This series of simple but definitive conclusions indicates that we have reached the stage of being able to precisely design molecular wires to attain desirable single-molecule electron conduction.
- Katagiri, Shunsuke,Sakamoto, Ryota,Maeda, Hiroaki,Nishimori, Yoshihiko,Kurita, Tomochika,Nishihara, Hiroshi
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p. 5088 - 5096
(2013/06/26)
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- The roles of molecular structure and effective optical symmetry in evolving dipolar chromophoric building blocks to potent octopolar nonlinear optical chromophores
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A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4′-, and 4′′-pos
- Ishizuka, Tomoya,Sinks, Louise E.,Song, Kai,Hung, Sheng-Ting,Nayak, Animesh,Clays, Koen,Therien, Michael J.
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supporting information; experimental part
p. 2884 - 2896
(2011/04/23)
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- Synthesis, spectroscopy, photophysics of multi-chromophoric ZN(II) group 8 metal complexes
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Novel multichromophoric complexes comprising the formula[in-line-formulae]R1—RA-[MC]-([RM]z-[MC])m-RA—R2[/in-line-formulae]are provided. Polymeric compositions and devices comprising the same are also discussed. The complexes are characterized by a central bridging moiety comprising one or a plurality of linked conjugated macrocyclic molecules [MC] coupled to at least one inorganic moiety (R1 and/or R2) through organic linker RA. Preparation methods include metal-mediated cross-coupling techniques. The complexes can be useful in nonlinear optical devices and other optoelectronic applications.
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Page/Page column 22-23; sheet 3
(2008/12/04)
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- Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores
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The syntheses and electrooptic properties of a new family of nonlinear optical chromophores are reported. These species feature an ethyne-elaborated, highly polarizable porphyrinic component and metal polypyridyl complexes that serve as integral donor and acceptor elements. Examples of this structural motif include ruthenium(II) [5-(4′-ethynyl-(2,2′;6′, 2″-terpyridinyl))-10,20-bis(2′,6′-bis(3, 3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)- (2,2′;6′,2″-terpyridine)2+ bis-hexafluorophosphate (Ru-PZn); osmium(II) [5-(4′-ethynyl-(2,2′;6′, 2″-terpyridinyl))-10,20-bis(2′,6′-bis(3, 3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2, 2′;6′,2″-terpyridine)2+ bis-hexafluorophosphate (Os-PZn); ruthenium(II) [5-(4′-ethynyl-(2,2′;6′, 2″-terpyridinyl))-15-(4′-nitrophenyl)ethynyl-10, 20-bis(2′,6′-bis(3,3-dimethyl-1-butyloxy) phenyl)porphinato]zinc(II)-(2,2′;6′, 2″-terpyridine)2+ bis-hexafluorophosphate (Ru-PZn-A); osmium(II) [5-(4′-ethynyl- (2,2′;6′,2″-terpyridinyl))-15- (4′-nitrophenyl)ethynyl-10,20-bis(2′, 6′-bis(3,3-dimethyl-1-butyloxy)phenyl) porphinato]zinc(II)-(2,2′;6′,2″-terpyridine)2+ bis-hexafluorophosphate (Os-PZn-A); and ruthenium(II) [5-(4′-ethynyl- (2,2′;6′,2″-terpyridinyl))osmium(II) -15-(4′-ethynyl-(2,2′;6′,2″-terpyridinyl))-10,20-bis (2′,6′-bis(3,3-dimethyl-1-butyloxy)phenyl) porphinato]zinc(Il)-bis(2,2′;6′, 2″-terpyridine)4+ tetrakis-hexafluorophosphate (Ru-PZn-Os). The frequency dependence of the dynamic hyperpolarizability of these compounds was determined from hyperRayleigh light scattering (HRS) measurements carried out at fundamental incident irradiation wavelengths (λinc) of 800, 1064, and 1300 nm. These data show that (i) coupled oscillator photophysics and metal-mediated cross-coupling can be exploited to elaborate high β0 supermolecules that exhibit significant excited-state electronic communication between their respective pigment building blocks; (ii) high-stability metal polypyridyl compounds constitute an attractive alternative to electron releasing dialkyl- and diarylamino groups, the most commonly used donor moieties in a wide range of established nonlinear optical dyes; (iii) this design strategy enables ready elaboration of chromophores having extraordinarily large dynamic hyperpolarizabilities (βλ values) at telecommunication relevant wavelengths; and (iv) porphyrin B- and Q-state-derived static hyperpolarizabilities (β0 values) can be designed to have the same or opposite sign in these species, thus providing a new means to regulate the magnitude of λinc-specific dynamic hyperpolarizabilities.
- Uyeda, H. Tetsuo,Zhao, Yuxia,Wostyn, Kurt,Asselberghs, Inge,Clays, Koen,Persoons, Andre,Therien, Michael J.
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p. 13806 - 13813
(2007/10/03)
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- The synthesis of 4′-aryl substituted terpyridines by Suzuki cross-coupling reactions: Substituent effects on ligand fluorescence
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Several 4′-aryl-substituted 2,2′:6′,2″-terpyridines (tpy-C6H4R) have been prepared by palladium-catalysed cross-coupling of 4′-bromoterpyridine or 4′-triflate-terpyridine (triflate = trifluoromethylsulfonyloxy) with aryl boronic acids or esters, RC6H4B(OR′)2 (R = H, m-NH2, p-CHO, -NO2, -CN, -NMe2, -NPh2). The new ligand 4′-mesityl-terpyridine (mesityl = 2,4,6-trimethylphenyl) was prepared in the same way. Similarly, 4′-bromophenylterpyridine (tpy-φ-Br) has been cross-coupled with aryl halides to generate several new biaryl-substituted terpyridines (tpy-φ-C6H4R where R = H, p-CN, NMe2, NPh2), together with two related compounds with pendent 3- or 4-pyridyl groups (tpy-φ-C6H4-py). For selected compounds, the alternative coupling strategy of reaction of a terpyridine-4-boronate or terpyridine-4-phenylboronate with the appropriate aryl halide has also been investigated (e.g. to prepare tpy-φ-C6H4NO2), but was generally found to be less satisfactory. All of the compounds are fluorescent in the UV region of the spectrum, the biaryl-substituted compounds being only slightly red-shifted compared to the monoaryl systems, but with the further red-shift that accompanies protonation being more significant for the former. Fluorescence lifetimes in solution are in the range 1-5 ns. The emission spectra of the aminobiphenyl-substituted compounds (tpy-φ-C6H4NR″2, where R″ = Me or Ph) display a large red-shift with increasing solvent polarity, suggesting the involvement of an intramolecular charge transfer state, as found previously for the two analogues omitting the phenyl ring (tpy-C6H4NR″2). In contrast to the latter, however, protonation or binding of a Lewis acidic metal ion to the aminobiphenyl compounds serves to quench almost completely their emission.
- Goodall, Wendy,Wild, Kerstin,Arm, Kathryn J.,Williams, J.A. Gareth
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p. 1669 - 1681
(2007/10/03)
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- Palladium-catalysed cross-coupling reactions of ruthenium bis-terpyridyl complexes: Strategies for the incorporation and exploitation of boronic acid functionality
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The palladium catalysed Miyaura cross-coupling reactions of 4′-(4-bromophenyl)-2,2′:6′,2″-terpyridine (tpy-φ-Br) and 4′-bromo-2,2′:6′,2″-terpyridine (tpy-Br) with bis(neopentyl glycolato)diboron (B2neo2 lead to the first reported exa
- Aspley,Williams
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p. 1136 - 1147
(2007/10/03)
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- From 1,2,4-triazines and tributyl(ethynyl)tin to stannylated bi- and terpyridines: The cycloaddition pathway
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Recently, we reported on cycloadditions between electron-deficient heterodienes and tributyl(ethynyl)tin, which provide a new pathway to stannylated pyridazines and, in one special case, pyridines. In order to broaden the synthetic scope of these reactions, we have developed hetero [4+2] cycloaddition reactions between a number of tailor-made 1,2,4-triazines 5-9 (acting as heterodienes), and tributyl(ethynyl)tin (acting as dienophile). The desired 1,2,4triazines are readily available, in moderate to very good yields, by the condensation reactions of appropiate carbamidrazones and glyoxals. These cycloadditions open up a novel route to regiospecifically stannylated 2,2'-bi- and 2,2',6',2''-terpyridines 1-4, 11 in good yields. The stannanes 1-4, 11 are versatile synthetic intermediates, and with this strategy various substituents can be incorporated directly by substitution of the stannyl group, as was shown for halogens and carbon electrophiles under Stille conditions.
- Sauer, Juergen,Heldmann, Dieter K.,Pabst, Gunther R.
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p. 313 - 321
(2007/10/03)
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- Ruthenium(II) complexes of some new polynucleating ligands incorporating terpyridyl and macrocyclic aza-crown binding sites
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A series of five new compounds has been prepared in which terpyridyl fragments are linked to hexadentate aza-crown macrocycles. Reaction of 1-aza-18-crown-6 (1,4,7,10,13-pentaoxa-16-azacyclooctadecane) and 1,10-diaza-18-crown-6 (1,4,10,13-tetraoxa-7,16-di
- Whittle, Brenda,Batten, Stuart R.,Jeffery, John C.,Rees, Leigh H.,Ward, Michael D.
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p. 4249 - 4255
(2007/10/03)
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- Preparation of Phosphonated Polypyridyl Ligands to anchor Transition-metal Complexes on Oxide Surfaces: Application for the Conversion of Light to Electricity with Nanocrystalline TiO2 Films
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To anchor transition-metal compounds onto metal oxide surfaces 2,2':6',2''-terpyridine-4'-phosphonic acid (4'-PO3H2-terpy) is synthesized; strong surface adhesion as well as efficient charge-transfer sensitization of nanocrystalline TiO2 films has been observed with a ruthenium complex involving this ligand.
- Pechy, Peter,Rotzinger, Francois P.,Nazeeruddin, Mohammed Khaja,Kohle, Oliver,Zakeeruddin, Shaik Mohammed,et al.
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