71071-46-0Relevant academic research and scientific papers
Factors Impacting Electron Transfer in Cyano-Bridged {Fe2Co2} Clusters
Zheng, Chunyang,Xu, Juping,Yang, Zhixin,Tao, Jun,Li, Dongfeng
, p. 9687 - 9689 (2015)
A cyano-bridged {FeIII2CoII2} complex exhibits reversible thermally and photoinduced intramolecular charge transfer. Its desolvated, MeOH-d4, and other analogues were compared to disclose the impact factors on the electron-transfer behavior of these {FeIII2CoII2} clusters.
Synthesis of Ortho-Functionalized 1,4-Cubanedicarboxylate Derivatives through Photochemical Chlorocarbonylation
Collin, Diego E.,Kovacic, Kristina,Light, Mark E.,Linclau, Bruno
, p. 5164 - 5169 (2021)
The cubane ring has received intense attention as a 3D benzene isostere and scaffold. Mono-and 1,4-disubstituted cubanes are well-described. Here we report a practical procedure for a direct radical-mediated chlorocarbonylation process initially reported by Bashir-Hashemi, to access a range of 2-substituted 1,4-cubanedicarboxylic ester derivatives. A subsequent regioselective ester hydrolysis to give fully differentiated 1,2,4-Trisubstituted cubanes is demonstrated.
Hetero-Bis-Conjugation of Bioactive Molecules to Half-Sandwich Ruthenium(II) and Iridium(III) Complexes Provides Synergic Effects in Cancer Cell Cytotoxicity
Batchelor, Lucinda K.,Biancalana, Lorenzo,Brabec, Viktor,Degano, Ilaria,Dyson, Paul J.,Hadiji, Mouna,Kostrhunova, Hana,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
, p. 9529 - 9541 (2021)
Four bipyridine-Type ligands variably derivatized with two bioactive groups (taken from ethacrynic acid, flurbiprofen, biotin, and benzylpenicillin) were prepared via sequential esterification steps from commercial 2,2′-bipyridine-4,4′-dicarboxylic acid and subsequently coordinated to ruthenium(II) p-cymene and iridium(III) pentamethylcyclopentadienyl scaffolds. The resulting complexes were isolated as nitrate salts in high yields and fully characterized by analytical and spectroscopic methods. NMR and MS studies in aqueous solution and in cell culture medium highlighted a substantial stability of ligand coordination and a slow release of the bioactive fragments in the latter case. The complexes were assessed for their antiproliferative activity on four cancer cell lines, showing cytotoxicity to the low micromolar level (equipotent with cisplatin). Additional biological experiments revealed a multimodal mechanism of action of the investigated compounds, involving DNA metalation and enzyme inhibition. Synergic effects provided by specific combinations of metal and bioactive fragments were identified, pointing toward an optimal ethacrynic acid/flurbiprofen combination for both Ru(II) and Ir(III) complexes.
Molecular engineered rhenium(i) carbonyl complexes to promote photoisomerization of coordinated stilbene-like ligands in the visible region
Amaral, Ronaldo C.,Murakami Iha, Neyde Y.
, p. 13081 - 13087 (2018)
Novel fac-[Re(CO)3(dmcb)(trans-stpyR)]+ complexes, dmcb = 4,4′-dimethoxycarbonyl-2,2′-bipyridine, have been judiciously engineered to absorb at lower energies and sensitize trans-4-styrylpyridine (trans-stpy) or trans-4-(4-cyano)styrylpyridine (trans-stpyCN) photoisomerizable ligands up to 436 nm of irradiation. Moreover, these complexes exhibit remarkable photoreversibility, in particular fac-[Re(CO)3(dmcb)(trans-stpyCN)]+ (Φ255 nmcis→trans = 0.26 ± 0.02). Their distinct and noteworthy photochemical and photophysical behavior are described in this work. The main emphasis of this study is that the complexes efficiently sensitize stilbene-like ligand isomerization toward use in potential solar device applications.
Synthesis, biomacromolecular interactions, photodynamic no releasing and cellular imaging of two [rucl(Qn)(lbpy)(no)]x complexes
Bai, Hehe,Gong, Wenjun,Liu, Chenyang,Song, Luna,Wang, Ai,Wang, Hongfei,Wang, Li,Zhao, Xuan,Zhao, Yi
, (2021)
Two light-activated NO donors [RuCl(qn)(Lbpy)(NO)]X with 8-hydroxyquinoline (qn) and 2,2′-bipyridine derivatives (Lbpy) as co-ligands were synthesized (Lbpy1 = 4,4′-dicarboxyl-2,2′-dipyridine, X = Cl? and Lbpy2 = 4,4′-dimethoxycarbonyl-2,2′-dipyridine, X = NO3? ), and characterized using ultraviolet–visible (UV-vis) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (1 H NMR), elemental analysis and electrospray ionization mass spectrometry (ESI-MS) spectra. The [RuCl(qn)(Lbpy2 )(NO)]NO3 complex was crystallized and exhibited distorted octahedral geometry, in which the Ru–N(O) bond length was 1.752(6) ? and the Ru–N–O angle was 177.6(6)? . Time-resolved FT-IR and electron paramagnetic resonance (EPR) spectra were used to confirm the photoactivated NO release of the complexes. The binding constant (Kb ) of two complexes with human serum albumin (HSA) and DNA were quantitatively evaluated using fluorescence spectroscopy, Ru-Lbpy1 (Kb ~106 with HSA and ~104 with DNA) had higher affinity than Ru-Lbpy2 . The interactions between the complexes and HSA were investigated using matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS) and EPR spectra. HSA can be used as a carrier to facilitate the release of NO from the complexes upon photoirradiation. The confocal imaging of photo-induced NO release in living cells was successfully observed with a fluorescent NO probe. Moreover, the photocleavage of pBR322 DNA for the complexes and the effect of different Lbpy substituted groups in the complexes on their reactivity were analyzed.
Redox Active Ion-Paired Excited States Undergo Dynamic Electron Transfer
Troian-Gautier, Ludovic,Beauvilliers, Evan E.,Swords, Wesley B.,Meyer, Gerald J.
, p. 16815 - 16826 (2016)
Ion-pair interactions between a cationic ruthenium complex, [Ru(dtb)2(dea)][PF6]2, C12+ where dea is 4,4′-diethanolamide-2,2′-bipyridine and dtb is 4,4′-di-tert-butyl-2,2′-bipyridine, and chloride, bromide, and iodide are reported. A remarkable result is that a 1:1 iodide:excited-state ion-pair, [C12+, I-]+*, underwent diffusional electron-transfer oxidation of iodide that did not occur when ion-pairing was absent. The ion-pair equilibrium constants ranged 104-106 M-1 in CH3CN and decreased in the order Cl- > Br- > I-. The ion-pairs had longer-lived excited states, were brighter emitters, and stored more free energy than did the non-ion-paired states. The1H NMR spectra revealed that the halides formed tight ion-pairs with the amide and alcohol groups of the dea ligand. Electron-transfer reactivity of the ion-paired excited state was not simply due to it being a stronger photooxidant than the non-ion-paired excited state. Instead, work term, ΔGw was the predominant contributor to the driving force for the reaction. Natural bond order calculations provided natural atomic charges that enabled quantification of ΔGw for all the atoms in C12+ and [C12+, I-]+* presented herein as contour diagrams that show the most favorable electrostatic positions for halide interactions. The results were most consistent with a model wherein the non-ion-paired C12+* excited state traps the halide and prevents its oxidation, but allows for dynamic oxidation of a second iodide ion.
Synthesis of novel tridentate pyrazole–bipyridine ligands for Co-complexes as redox-couples in dye-sensitized solar cells
Zavozin, Alexander G.,Ignat'ev, Nikolai V.,Schulte, Michael,Zlotin, Sergei G.
, p. 8551 - 8556 (2015)
Novel pyrazole bipyridine ligands have been synthesized from 4,4′-substituted bipyridines through oxidation, chlorination and non-catalyzed C–N coupling of potassium pyrazolate with 6-halogen-4,4′-bipyridines in diglyme. These tridentate pyrazole–bipyridine ligands are of interest as components of new redox systems for dye-sensitized solar cells.
Dimethyl 2,2′-bipyridine-6,6′-dicarboxyl-ate and bis-(dimethyl 2,2′-bipyridine-6,6′-dicarboxyl-ato-2 N,N′)copper(I) tetra-fluoro-borate
Blake, Alexander J.,Champness, Neil R.,Mason, Pamela V.,Wilson, Claire
, p. m280-m282 (2007)
The single-crystal X-ray structures of dimethyl 2,2′-bipyridine-6, 6′-dicarboxylate, C14H12N2O4, and the copper(I) coordination complex bis-(dimethyl 2,2′-bipyridine-6,6′-dicarboxylato-2 N,N′)copper(I) tetra-fluoro-borate, [Cu(C14H12N2O4)2]BF4, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anti-cipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter-pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′-bipyridine. International Union of Crystallography 2007.
A Systematic Study of the Effects of Complex Structure on Aryl Iodide Oxidative Addition at Bipyridyl-Ligated Gold(I) Centers
Bower, John F.,Cadge, Jamie A.,Russell, Christopher A.
supporting information, p. 24976 - 24983 (2021/10/20)
A combined theoretical and experimental approach has been used to study the unusual mechanism of oxidative addition of aryl iodides to [bipyAu(C2H4)]+ complexes. The modular nature of this system allowed a systematic assessment of the effects of complex structure. Computational comparisons between cationic gold and the isolobal (neutral) Pd0 and Pt0 complexes revealed similar mechanistic features, but with oxidative addition being significantly favored for the group 10 metals. Further differences between Au and Pd were seen in experimental studies: studying reaction rates as a function of electronic and steric properties showed that ligands bearing more electron-poor functionality increase the rate of oxidative addition; in a complementary way, electron-rich aryl iodides give faster rates. This divergence in mechanism compared to Pd suggests that Ar?X oxidative addition with Au can underpin a broad range of new or complementary transformations.
Double-ligand nitrosyl ruthenium complex as well as preparation method and application thereof
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Paragraph 0017-0018, (2021/10/20)
The invention belongs to the technical field of preparation of nitrosylruthenium complex, and relates to a double-ligand nitrosyl ruthenium complex and a preparation method and application thereof. The chemical formula of the double-ligand nitrosyl ruthenium complex is [RuCl (qn) (Lbpy) (NO)] NO. 3 , qn Is 8 -hydroxyquinoline, Lbpy is 2,2 '-bipyridine -4, 4' - dimethyl formate and the structural formula thereof is shown in the specification. The obtained complex has high purity and low cytotoxicity, and has certain water solubility and sensitive photodynamic activity. Experimental detection shows that the complex can quantitatively regulate the release of nitric oxide through photoexcitation, and can be applied to nitric oxide donors in a nitric oxide donor and cell system in a solution system for preparing light regulation and control.
