- Tris(rhenium fac-tricarbonyl) Polypyridine Functionalized Cyclotriguaiacylene Ligands with Rich and Varied Emission
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Trinuclear rhenium fac-tricarbonyl bromide complexes have been synthesized coordinated to the host ligands tris(4-[4-methyl-2,2′-bipyridyl]methyl)cyclotriguaiacylene (L1), tris(4-[4-methyl-2,2′-bipyridoyl])cyclotriguaiacylene (L2), and tris(4-[2,2′,6′,2″-terpyridyl]benzyl)cyclotriguaiacylene (L3). The structure of L1 and complexes [{Re(CO)3Br}3(L1)] (1) and [{Re(CO)3Br}3(L3)] (3) have been elucidated through X-ray single-crystal diffraction, with complex 3 crystallizing as a conglomerate. The steady-state luminescent properties and time-resolved fluorescence studies of the complexes have been conducted and revealed an unusual dual-emission phenomenon for complex 2. Complexes 1 and 2 show red-shifted emission wavelengths in comparison with those typical of monometallic Re(CO)3-bipy-Br complexes, while complex 3 showed an unusual excitation-dependent variation of emission wavelength.
- Thorp-Greenwood, Flora L.,Pritchard, Victoria E.,Coogan, Michael P.,Hardie, Michaele J.
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- Synthesis, electrochemical, and photophysical studies of multicomponent systems based on porphyrin and ruthenium(II) polypyridine complexes
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Two ruthenium tris-bipyridine functionalized porphyrins 4, 8 and their Zn derivatives 4-Zn, 8-Zn were designed, synthesized, and characterized. The redox potentials of these complexes as well as their corresponding monomeric reference porphyrin and ruthen
- Liu, Xien,Liu, Jianhui,Pan, Jingxi,Andersson, Samir,Sun, Licheng
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- Metal-organic approach to binary optical memory
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Two new Ru(II) diimine chromophores, each containing a single photochromic dianthryl unit, have been prepared and characterized. The photoluminescence from the Ru(II) complexes is modulated by the photochromic action of the dianthryl species, which serves as a triplet energy transfer quencher in one photochromic state. The coupling of the dianthryl photochromic action to the Ru(II) complex emission permits nondestructive photoluminescence readout of binary information photochemically recorded on the molecular level. Luminescent images stored on polystyrene films that contain these molecules maintained their integrity for periods of months with no apparent degradation or variation in the image resolution, suggesting their durability for long-term storage in read-only memory applications. Copyright
- Tyson, Daniel S.,Bignozzi, Carlo A.,Castellano, Felix N.
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- Photoinduced electron transfer in amino acid assemblies
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The preparation and photophysical characterization of a of redox-active lysines and related model compounds based on polypyridyl ruthenium complexes are described. Donor-chromophore-acceptor triad 1, [PTZpn-Lys(RuIIb2m)2+-NH-prPQ2+] (PF6-)4 (see below), by of a bipyridyl caromophore (RuIIb2m, where b = 2,2′-bipyridine, m = 4′-methyl-2,2′-bipyridyl-4′-carbonyl), an electron donor (phenothiazine, PTZ), and an (paraquat, PQ2+) on a (Lys) scaffold utilizing bonds. This derivatized amiono acid exihibited efficient (>95%) quenching of the ruthenium metal-to-ligand charge-transfer (MLCT) excited state upon irradiation with a 420-nm laser pulse in CH3CN. The resulting state, [(PTZpn+)-Lys(RuIIb2m) 2+-NH-(prPQ+)]) 1.17 eV and lived for 108 ns (k = 9.26 × 106 s-1) as observed by transient absorption spectrosoopy. Also studied was a of related model systems that included model chroaophores, simple chromophore-quencher dyads linked by amide bonds, and chromophore-queneher dyads on lysine. An account of the of kinetic behavior of these system including triad 1 and a discussion of factors that influence the lifetime of the redox-separated states, their efficiency of formation, their energy storage ability are presented.
- Mecklenburg, Sandra L.,Peek, Brain M.,Schoonover, Jon R.,McCafferty, Dewey G.,Wall, Craig G.,Erickson, Bruce W.,Meyer, Thomas J.
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- A novel ruthenium(II) tris(bipyridine)-zinc porphyrin-rhenium carbonyl triad: Synthesis and optical properties
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A novel ruthenium(II) tris(bipyridine)-zinc porphyrin-rhenium carbonyl triads and its free base porphyrin derivative were synthesized and characterized by 1H, 13C NMR, UV-vis, mass-spectrometry and elemental analysis. The redox poten
- Liu, Xien,Liu, Jianhui,Pan, Jingxi,Chen, Ruikui,Na, Yong,Gao, Weiming,Sun, Licheng
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- Synthesis, characterization and some properties of amide-linked porphyrin-ruthenium(II) tris(bipyridine) complexes
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A new molecular dyad, comprised of a zinc-porphyrin and a ruthenium(II) tris(bipyridine) complex linked through an amide bond has been synthesized and characterized by 1H, 13C NMR, UV-vis, mass-spectrometry and elemental analysis. The electrochemistry as well as the steady-state emission properties were investigated. The redox behavior of the dyad exhibits a favorable reversible characteristic. Substantial quenching of porphyrin emission was found when the Q band of 5 and 5-Zn was selectively photoexcited. This observation suggests a quenching mechanism with possible intramolecular electron transfer or energy transfer between the Ru(bpy)3 moiety and the porphyrin free-base or Zn porphyrin moieties.
- Liu, Xien,Liu, Jianhui,Jin, Kun,Yang, Xichuan,Peng, Qinji,Sun, Licheng
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- Re(I) sensitised near-infrared lanthanide luminescence from a hetero-trinuclear Re2Ln array
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The trinuclear complexes Re2Ln (Ln = Nd, Yb or Er) contain two ReI tricarbonyl units linked to a DTPA binding site via 2,2′-bipyridyl ligands; LnIII-centred emission is sensitised by the ReI MLCT excited states.
- Pope, Simon J. A.,Coe, Benjamin J.,Faulkner, Stephen
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- Synthesis, Characterization and Photochromic Studies of Spirooxazine-Containing 2,2′-Bipyridine Ligands and Their Rhenium(I) Tricarbonyl Complexes
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A series of spirooxazine-containing 2,2′-bipyridine ligands and their rhenium(I) tricarbonyl complexes has been designed and synthesized, and their photophysical, photochromic and electrochemical properties have been studied. The X-ray crystal structures
- Ko, Chi-Chiu,Wu, Li-Xin,Wong, Keith Man-Chung,Zhu, Nianyong,Yam, Vivian Wing-Wah
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- Bioactive half-sandwich Rh and Ir bipyridyl complexes containing artemisinin
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Reaction of dihydroartemisinin (DHA) with 4-methyl-4′-carboxy-2,2′-bipyridine yielded the new ester derivative L1. Six novel organometallic half-sandwich chlorido Rh(III) and Ir(III) complexes (1–6) containing pentamethylcyclopentadienyl, (Cp*), tetramethylphenylcyclopentadienyl (Cpxph), or tetramethylbiphenylcyclopentadienyl (Cpxbiph), and N,N-chelated bipyridyl group of L1, have been synthesized and characterized. The complexes were screened for inhibitory activity against the Plasmodium falciparum 3D7 (sensitive), Dd2 (multi-drug resistant) and NF54 late stage gametocytes (LSGNF54), the parasite strain Trichomonas vaginalis G3, as well as A2780 (human ovarian carcinoma), A549 (human alveolar adenocarcinoma), HCT116 (human colorectal carcinoma), MCF7 (human breast cancer) and PC3 (human prostate cancer) cancer cell lines. They show nanomolar antiplasmodial activity, outperforming chloroquine and artemisinin. Their activities were also comparable to dihydroartemisinin. As anticancer agents, several of the complexes showed high inhibitory effects, with Ir(III) complex 3, containing the tetramethylbiphenylcyclopentadienyl ligand, having similar IC50 values (concentration for 50% of maximum inhibition of cell growth) as the clinical drug cisplatin (1.06–9.23 μM versus 0.24–7.2 μM, respectively). Overall, the iridium complexes (1–3) are more potent compared to the rhodium derivatives (4–6), and complex 3 emerges as the most promising candidate for future studies.
- Chellan, Prinessa,Avery, Vicky M.,Duffy, Sandra,Land, Kirkwood M.,Tam, Christina C.,Kim, Jong H.,Cheng, Luisa W.,Romero-Canelón, Isolda,Sadler, Peter J.
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- Synthesis, Characterization, and Photochromic Studies of Cyclometalated Iridium(III) Complexes Containing a Spironaphthoxazine Moiety
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A series of cyclometalated iridium(III) complexes has been designed and synthesized, and their photophysical, photochromic, and electrochemical properties have been studied. The X-ray crystal structure of complex 2 has been determined. The emission properties of the complexes have been shown to be readily perturbed through the modification of the electronic properties of the phenylpyridine ligand. With different substituents at the phenylpyridine ligand of iridium(III) complexes of 1 (-H), 2 (-OMe), 3 (-CHO), and 4 (-CF3), they can display intense 3MLCT [dπ(Ir) → π*(diimine)] luminescence from 530 to 640 nm to span across the green to orange region. The spectral assignment is also in agreement with the electrochemical studies and DFT calculations. In addition, the photochromic behavior can be easily modulated by varying the substituents on the C∧N ligand without the need for tedious modification of the spirooxazine framework. By analyzing the kinetic profiles of backward bleaching reactions, less electron-rich iridium(III) complexes can stabilize the merocyanine form with a higher activation barrier. The studies have provided not only fundamental understanding on structure-property relationships that govern the versatile luminescence behavior of these Ir(III) complexes but also the guiding principles in the molecular design for the future developments of visible light-driven photoswitches.
- Liu, Jie,Chan, Alan Kwun-Wa,Ng, Maggie,Hong, Eugene Yau-Hin,Wu, Nathan Man-Wai,Wu, Lixin,Yam, Vivian Wing-Wah
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- Photoelectrochemical properties of dyads composed of porphyrin/ruthenium catalyst grafted on metal oxide semiconductors
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In the current work, we present the use of two free-base and two zinc-metallated porphyrin-ruthenium(II) polypyridine dyads, along with two reference porphyrin derivatives, as sensitizers in both n- and p-type DSSCs and DSPECs. Two of the dyads contain th
- Charalambidis, Georgios,Charisiadis, Asterios,Coutsolelos, Athanassios G.,Glymenaki, Eleni,Lavergne-Bril, Anna-Caroline,Margiola, Sofia,Nikolaou, Vasilis,Nikoloudakis, Emmanouil,Odobel, Fabrice,Planchat, Aurélien
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- Metal-to-ligand charge-transfer sensitisation of near-infrared emitting lanthanides in trimetallic arrays M2Ln (M = Ru, Re or Os; Ln = Nd, Er or Yb)
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The new pro-ligand 4-methyl-4'-(carbonylaraino(2-(tert-butoxycarbonylamino) ethyl))-2,2'-bipyridyl (L1) has been prepared and used to synthesise the complex fac-ReICl(CO)3(L1) 1 and the complex salts [MII(bipy)2(L1)](PF 6)2 (M = RuII 8 or OsII 15). Deprotection with trifluoroacetic acid affords the amine-functionalised derivatives fac-ReICl(CO)3(L2) 2, [M II(bipy)2(L2)](PF6)2 (M = RuII 9 or OsII 16) which react with the dianhydride of diethylenetriamine pentaacetic acid (DTPA) to give the binuclear complex {fac-ReICl(CO)3}2(L3) 3 and the complex salts [{MII(bipy)2}2(L 3)](PF6)4 (M = RuII 10 or Os II 17). The latter react with salts Ln(OTf)3 to afford a series of 12 heterotrimetallic compounds that contain a lanthanide (Ln) ion in the DTPA binding site; {fac-ReICl(CO)3}2(L 3)LnIII (Ln = Nd 4, Er 5, Yb 6 or Y 7) and [{M II(bipy)2}2(L3)Ln III](PF6)(OTf)3 (M = RuII, Ln = Nd 11, Er 12, Yb 13 or Y 14; M = OsII, Ln = Nd 18, Er 19, Yb 20 or Y 21). All of these trimetallic species display absorption bands ascribed to metal-to-ligand charge-transfer (MLCT) excitations, and luminescence measurements show that these excited states can be used to sensitise near-infrared emission from LnIII (Ln = Nd, Er or Yb) ions. Single crystal X-ray structures of LI and [RuII(bipy) 2(L2H)](H2PO4)3· (CH3)2CO·0.8H2O were obtained, the latter revealing the presence of H2PO4- counter anions, the source of which is presumed to be hydrolysis of PF6 - ions. The Royal Society of Chemistry 2005.
- Pope, Simon J. A.,Coe, Benjamin J.,Faulkner, Stephen,Laye, Rebecca H.
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- A Multi-action and Multi-target RuII–PtIV Conjugate Combining Cancer-Activated Chemotherapy and Photodynamic Therapy to Overcome Drug Resistant Cancers
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PtII complexes are commonly used to treat cancer. To reduce their side effects and improve their pharmacological properties, PtIV complexes are being developed as prodrug candidates that are activated by reduction in cancer cells. Concomitantly, RuII polypyridine complexes have gained much attention as photosensitizers for use in photodynamic therapy due to their attractive characteristics. In this article, a novel PtIV–RuII conjugate, which combines cancer activated chemotherapy with PDT, is presented. Upon entering the cancer cell, the PtIV centre is reduced to PtII and the axial ligands including the RuII complex and phenylbutyrate are released. As each component has its individual targets, the conjugate exerts a multi-target and multi-action effect with (photo-)cytotoxicity values upon irradiation up to 595 nm in the low nanomolar range in various (drug resistant) 2D monolayer cancer cells and 3D multicellular tumour spheroids.
- Gasser, Gilles,Gibson, Dan,Karges, Johannes,Tharaud, Micka?l,Yempala, Thirumal
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supporting information
p. 7069 - 7075
(2020/03/16)
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- Postmodification of a supramolecular organic framework: Visible-light-induced recyclable heterogeneous photocatalysis for the reduction of azides to amines
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We present the postmodification of a diamondoid 3D supramolecular organic framework (SOF) to append [Ru(BPY)3]2+ groups through the formation of a hydrazone bond. The resulting SOF works as an efficient recyclable heterogeneous catalyst for visible-light-induced reduction of aromatic azides to amines.
- Wu, Yi-Peng,Yang, Bo,Tian, Jia,Yu, Shang-Bo,Wang, Hui,Zhang, Dan-Wei,Liu, Yi,Li, Zhan-Ting
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supporting information
p. 13367 - 13370
(2017/12/26)
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- Detection of NaCN in aqueous media using a calixarene-based fluoroionophore containing ruthenium(ii)-bipyridine as the fluorogenic unit
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A new molecular sensor containing calixarene and ruthenium(ii)-bipyridine as the fluorophore bridged by an amide moiety has been synthesised and characterized, and its anion binding properties have been investigated. It selectively detected cyanide in 95:5 water:acetonitrile when sodium salts of various anions such as F-, Cl-, Br-, I-, PO42-, IO4-, BO3-, CH3COO-, CN- and SO42- were investigated. The recognition event was monitored by fluorescence spectroscopy and the lower detection limit found was 70 ppb. However, when tetrabutylammonium salts of the same anions were used then, in addition to CN-, CH3COO- was also detected under similar experimental conditions. Interestingly, CN- exhibited substantial quenching, whereas CH3COO- showed an enhancement in emission intensity. The interaction of anions with the fluoroionophore was also monitored by electrochemical technique and the result obtained is consistent to that found by fluorogenic method. Binding constants were determined from emission titration, composition of the anion-complexes formed were determined from mass and emission titration data, mechanistic aspects of the interaction have been discussed with the aid of NMR data and the role of cations in the contrast fluorescent off and on behaviour has also been discussed. This sensor has also been used to estimate cyanide in real samples and the result obtained is satisfactory. This journal is
- Maity, Debdeep,Vyas, Gaurav,Bhatt, Madhuri,Paul, Parimal
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p. 6151 - 6159
(2015/03/05)
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- Proton-coupled electron transfer from tyrosine: A strong rate dependence on intramolecular proton transfer distance
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Proton-coupled electron transfer (PCET) was examined in a series of biomimetic, covalently linked RuII(bpy)3-tyrosine complexes where the phenolic proton was H-bonded to an internal base (a benzimidazyl or pyridyl group). Photooxidation in laser flash/quench experiments generated the RuIII species, which triggered long-range electron transfer from the tyrosine group concerted with short-range proton transfer to the base. The results give an experimental demonstration of the strong dependence of the rate constant and kinetic isotope effect for this intramolecular PCET reaction on the effective proton transfer distance, as reflected by the experimentally determined proton donor-acceptor distance.
- Zhang, Ming-Tian,Irebo, Tania,Johansson, Olof,Hammarstroem, Leif
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supporting information; experimental part
p. 13224 - 13227
(2011/10/10)
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- Interfacial electron transfer dynamics of two newly synthesized catecholate bound RuII polypyridyl-based sensitizers on TiO2 nanoparticle surface - A femtosecond pump probe spectroscopic study
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Two new catecholate-bound RuII-polypyridine based sensitizers, (2,2′-bipyridine){ethyl 3-(4-hydroxyphenyl)-2-[(4′-methyl-2, 2′-bipyridinyl-4-carbonyl)amino]propionate}{4-[2-(4′-methyl-2, 2′-bipyridinyl-4-yl)vinyl]benzene-1,2-diol)}ruthenium(II) hexafluorophosphate (5) and [(2,2′-bipyridine)-(4-2,2′-bipyridinyl- 4-yl-phenol)-(4-{2-(4′-methyl-2,2′-bipyridinyl-4-yl)vinyl}benzene-1, 2-diol)]ruthenium(II) hexafluorophosphate (6) with secondary electron-donating groups (tyrosine and phenol, respectively) were synthesized and characterized. Steady-state optical absorption and emission studies confirm strong coupling between the sensitizers and TiO2 nanoparticles. Femtosecond visible transient absorption spectroscopy has been employed to study interfacial electron transfer (IET) dynamics in the dye-nanoparticle systems to explore the influence of the secondary electron-donating groups on IET dynamics. Electron injection into the conduction band of nanoparticulate TiO2 has been confirmed by detection of the conduction band electrons in TiO2 ([e-]TiO2CB) and radical cation of the adsorbed dye (D·+) in real time monitored by transient absorption spectroscopy. A single exponential and pulse-width limited (2 and by the recovery of the ground state bleach. BET dynamics in dye-TiO2 systems for complexes 5 and 6 have been compared with those of [bis(2,2′-bpy)-(4-{2-(4′-methyl-2, 2′-bipyridinyl-4-yl)vinyl}benzene-1,2-diol)]ruthenium(II) hexafluorophosphate (7), which does not have a secondary electron-donating group.
- Banerjee, Tanmay,Rawalekar, Sachin,Das, Amitava,Ghosh, Hirendra N.
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experimental part
p. 4187 - 4197
(2011/12/05)
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- Synthesis of ligands based on 4H-imidazoles and pyridine subunits: Selective complexation and bathochromically absorbing complexes
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New multifunctional ligands based on the combination of 4H-imidazoles with pyridine subunits have been synthe-sised. The long wavelength absorptions originating from the merocyanine-chromophore can be shifted towards the near infrared (MR) region by introduction of additional auxochromic groups. Due to different complexation spheres these hybrid-ligands form the requirements for the construction of heterobimetallic complexes. In addition, the hybrid ligands are redox active compounds showing two separated fully reversible reductions.
- Blumhoff, Joerg,Beckert, Rainer,Rau, Sven,Losse, Sebastian,Matschke, Martin,Guenther, Wolfgang,Goerls, Helmar
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experimental part
p. 2162 - 2169
(2009/09/05)
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- Remote site photosubstitution in metalloporphyrin-rhenium tricarbonylbipyridine assemblies: Photo-reactions of molecules with very short lived excited states
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The synthesis is reported of a series of metalloporphyrins (and the corresponding free-base porphyrin), mono-meso-substituted with a bipyridyl group via an amide link at the 4-position of one phenyl group: [Re(CO) 3(Pic)Bpy-MTPP][OTf], where M = Mg, Zn, Pd or 2H, Pic = 3-picoline, Bpy = 2,2′-bipyridine, TPP = tetraphenylporphyrin. The photochemical reactions of the assemblies with the sacrificial electron donor triethylamine have been investigated by IR spectroscopy and compared to the behaviour of analogues of the type Bpy-MTPP without rhenium. Selective long-wavelength irradiation of the metalloporphyrin unit in the presence of excess picoline leads to reduction at the rhenium bipyridine centre. In the absence of 3-picoline, the latter is not reduced, but substituted by added halide or by the THF solvent. Mechanistic analysis highlights the differences between the zinc and magnesium chelate on the one hand and the palladium porphyrin on the other. The free-base assembly, [Re(CO)3(Pic)Bpy-H2TPP][OTf] is unreactive. The zinc and magnesium porphyrin assemblies initially coordinate Et3N before undergoing photo-induced inner-sphere electron transfer from the triethylamine to form a charge-shifted excited state of the assembly. In contrast, the palladium-based dyad reacts via outer-sphere reductive quenching of a porphyrin-based excited state. The substitution products are postulated to form by a mechanism involving an electron-transfer chain.
- Gabrielsson, Anders,Lindsay Smith, John R.,Perutz, Robin N.
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experimental part
p. 4259 - 4269
(2009/02/03)
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- Ultrafast charge separation in a photoreactive rhenium-appended porphyrin assembly monitored by picosecond transient infrared spectroscopy
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Rhenium(bipyridine)(tricarbonyl)(picoline) units have been linked covalently to tetraphenylmetalloporphyrins of magnesium and zinc via an amide bond between the bipyridine and one phenyl substituent of the porphyrin. The resulting complexes, abbreviated a
- Gabrielsson, Anders,Hartl, Frantisek,Zhang, Hong,Smith, John R. Lindsay,Towrie, Michael,Vicek Jr., Antonin,Perutz, Robin N.
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p. 4253 - 4266
(2007/10/03)
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- Aryl-diamide bridged binuclear ruthenium (II) tris(bipyridine) complexes: Synthesis, photophysical, electrochemical and electrochemiluminescence properties
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Several new symmetrical aromatic hydrocarbon bridged bipyridine ligands and their binuclear Ru (II) complexes have been designed, synthesized and characterized on the basis of 1H NMR, MS and HRMS. Their absorption and emission properties, elect
- Li, Minna,Liu, Jianhui,Zhao, Changzhi,Sun, Licheng
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p. 4189 - 4195
(2007/10/03)
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- Systematic synthesis and photochemistry of tetraaryl porphyrins mono-substituted with a transition metal carbonyl: characterisation of a zinc porhyrin-rhenium carbonyl complex
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A systematic synthesis designed to connect a metalloporphyrin to a metal carbonyl moiety is demonstrated through a zinc tetraphenyl porphyrin substituted with Re(CO)3(4'-methyl-2,2'-bipyridyl)Br via an amide bond; the emission and excited state absorption spectra are dominated by porphyrin transitions.
- Aspley, Catherine J.,Smith, John R. Lindsay,Perutz, Robin N.
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p. 2269 - 2272
(2007/10/03)
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- Novel anion binding selectivity trends exhibited by new dinuclear rhenium(I), ruthenium(II) and osmium(II) bipyridyl cleft-type receptors
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Novel dinuclear rhenium(I), ruthenium(II) and osmium(II) bipyridyl cleft-type receptor systems exhibit remarkable selectivity for dihydrogenphosphate over halide anions dictated by the nature of the bridging linkage and the transition-metal Lewis-acidic centre.
- Beer, Paul D.,Dent, Simon W.,Hobbs, Gerald S.,Wear, Trevor J.
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- Diporphyrinyl Derivatives of 1,10-Phenanthroline and 2,2'-Bipyridyl
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The title derivatives were synthesized containing two meso-tri-p-tolylphenyleneporphyrin units attached via amide bridges to 4,7- and 4,4' positions of the respective heteroatomatic spacers.
- Kus, Piotr,Knerr, Gary,Czuchajowski, Leszek
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