Dataset Information

Synthesis and Light-Induced Actuation of Photo-Labile 2-Pyridyl-1,2,3-Triazole Ru(bis-bipyridyl) Appended Ferrocene Rotors.

ABSTRACT: To realise useful control over molecular motion in the future an extensive toolbox of both actionable molecules and stimuli-responsive units must be developed. Previously, our laboratory has reported 1,1'-disubstituted ferrocene (Fc) rotor units which assume a contracted/?-stacked conformation until complexation of cationic metal ions causes rotation about the Ferrocene (Fc) molecular 'ball-bearing'. Herein, we explore the potential of using the photochemical ejection of [Ru(2,2'-bipyridyl)?]2+ units as a stimulus for the rotational contraction of new ferrocene rotor units. Fc rotors with both 'regular' and 'inverse' 2-pyridyl-1,2,3-triazole binding pockets and their corresponding [Ru(2,2'-bipyridyl)?]2+ complexes were synthesised. The rotors and complexes were characterised using nuclear magnetic resonance (NMR) and ultraviolet (UV)-visible spectroscopies, Electro-Spray Ionisation Mass Spectrometry (ESI?MS), and electrochemistry. The 1,1'-disubstituted Fc ligands were shown to ?-stack both in solution and solid state. Density Functional Theory (DFT) calculations (CAM-B3LYP/6-31G(d)) support the notion that complexation to [Ru(2,2'-bipyridyl)?]2+ caused a rotation from the syn- to the anti-conformation. Upon photo-irradiation with UV light (254 nm), photo-ejection of the [Ru(2,2'-bipyridyl)?(CH?CN)?]2+ units in acetonitrile was observed. The re-complexation of the [Ru(2,2'-bipyridyl)?]2+ units could be achieved using acetone as the reaction solvent. However, the process was exceedingly slowly. Additionally, the Fc ligands slowly decomposed when exposed to UV irradiation meaning that only one extension and contraction cycle could be completed.

SUBMITTER: Findlay JA

PROVIDER: S-EPMC6222349 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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Publications

Synthesis and Light-Induced Actuation of Photo-Labile 2-Pyridyl-1,2,3-Triazole Ru(bis-bipyridyl) Appended Ferrocene Rotors.

Findlay James A JA Barnsley Jonathan E JE Gordon Keith C KC Crowley James D JD

Molecules (Basel, Switzerland) 20180814 8

To realise useful control over molecular motion in the future an extensive toolbox of both actionable molecules and stimuli-responsive units must be developed. Previously, our laboratory has reported 1,1'-disubstituted ferrocene (Fc) rotor units which assume a contracted/π-stacked conformation until complexation of cationic metal ions causes rotation about the Ferrocene (Fc) molecular 'ball-bearing'. Herein, we explore the potential of using the photochemical ejection of [Ru(2,2'-bipyridyl)₂]<su ...[more]

PMID: 30110981

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Project description:Molecular switching processes are important in a range of areas including the development of molecular machines. While there are numerous organic switching systems available, there are far less examples that exploit inorganic materials. The most common inorganic switching system remains the copper(I)/copper(II) switch developed by Sauvage and co-workers over 20 years ago. Herein, we examine if bidentate 2-(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine (pytri) and tridentate 2,6-bis[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]pyridine (tripy) moieties can be used to replace the more commonly exploited polypyridyl ligands 2,2'-bypyridine (bpy)/1,10-phenanthroline (phen) and 2,2';6',2″-terpyridine (terpy) in a copper(I)/(II) switching system. Two new ditopic ligands that feature bidentate (pytri, L1 or bpytri, L2) and tridentate tripy metal binding pockets were synthesized and used to generate a family of heteroleptic copper(I) and copper(II) 6,6'-dimesityl-2,2'-bipyridine (diMesbpy) complexes. Additionally, we synthesized a series of model copper(I) and copper(II) diMesbpy complexes. A combination of techniques including nuclear magnetic resonance (NMR) and UV-vis spectroscopies, high-resolution electrospray ionization mass spectrometry, and X-ray crystallography was used to examine the behavior of the compounds. It was found that L1 and L2 formed [(diMesbpy)Cu(L1 or L2)]2+ complexes where the copper(II) diMesbpy unit was coordinated exclusively in the tridenate tripy binding site. However, when the ligands (L1 and L2) were complexed with copper(I) diMesbpy units, a complex mixture was obtained. NMR and MS data indicated that a 1:1 stoichiometry of [Cu(diMesbpy)]+ and either L1 or L2 generated three complexes in solution, the dimetallic [(diMesbpy)2Cu2(L1 or L2)]2+ and the monometallic [(diMesbpy)Cu(L1 or L2)]+ isomers where the [Cu(diMesbpy)]+ unit is coordinated to either the bidentate or tridentate tripy binding sites of the ditopic ligands. The dimetallic [(diMesbpy)2Cu2(L1 or L2)](PF6)2 complexes were structurally characterized using X-ray crystallography. Both complexes feature a [Cu(diMesbpy)]+ coordinated to the bidentate (pytri or bpytri) pocket of the ditopic ligands (L1 or L2), as expected. They also feature a second [Cu(diMesbpy)]+ coordinated to the nominally tridentate tripy binding site in a four-coordinate hypodentate κ2-fashion. Competition experiments with model complexes showed that the binding strength of the bidentate pytri is similar to that of the κ2-tripy ligand, leading to the lack of selectivity. The results suggest that the pytri/tripy and bpytri/tripy ligand pairs cannot be used as replacements for the more common bpy/phen-terpy partners due to the lack of selectivity in the copper(I) state.

Dataset Information

Synthesis and Light-Induced Actuation of Photo-Labile 2-Pyridyl-1,2,3-Triazole Ru(bis-bipyridyl) Appended Ferrocene Rotors.

Publications

Synthesis and Light-Induced Actuation of Photo-Labile 2-Pyridyl-1,2,3-Triazole Ru(bis-bipyridyl) Appended Ferrocene Rotors.

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