Rhenium tricarbonyl complexes of 1-benzyl-4-(5-bipyridyl)-1H-1,2,3-triazoles

Cote, Catherine; Kirss, Rein U.

doi:10.1016/j.ica.2010.04.019

Cited by 9 publications

(5 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The possible influence of these modes was not included in calculations. These modes are antisymmetric stretching modes of the three carbonyl modes on the Re complex headgroup. , Coupled normal modes can undergo rapid equilibration (intramolecular vibrational excitation transfer) on a picosecond time scale. Equilibration of population between the vibrational modes would result in biexponential decays.…”

Section: Resultsmentioning

confidence: 99%

Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy

et al. 2012

View full text Add to dashboard Cite

The structural dynamics of thin films consisting of tricarbonyl (1,10-phenanthroline)rhenium chloride (RePhen(CO)3Cl) linked to an alkyl silane monolayer through a triazole linker synthesized on silica-on-calcium-fluoride substrates are investigated using ultrafast infrared (IR) techniques. Ultrafast 2D IR vibrational echo experiments and polarization selective heterodyne detected transient grating (HDTG) measurements, as well as polarization dependent FT-IR and AFM experiments are employed to study the samples. The vibrational echo experiments measure spectral diffusion, while the HDTG experiments measure the vibrational excited state population relaxation and investigate the vibrational transition dipole orientational anisotropy decay. To investigate the anticipated impact of vibrational excitation transfer, which can be caused by the high concentration of RePhen(CO)3Cl in the monolayer, a concentration dependence of the spectral diffusion is measured. To generate a range of concentrations, mixed monolayers consisting of both hydrogen terminated and triazole/RePhen(CO)3Cl terminated alkyl silanes are synthesized. It is found that the measured rate of spectral diffusion is independent of concentration, with all samples showing spectral diffusion of 37 ± 6 ps. To definitively test for vibrational excitation transfer, polarization selective HDTG experiments are conducted. Excitation transfer will cause anisotropy decay. Polarization resolved heterodyne detected transient grating spectroscopy is sensitive to anisotropy decay (depolarization) caused by excitation transfer and molecular reorientation. The HDTG experiments show no evidence of anisotropy decay on the appropriate time scale, demonstrating the absence of excitation transfer the RePhen(CO)3Cl. Therefore the influence of excitation transfer on spectral diffusion is inconsequential in these samples, and the vibrational echo measurements of spectral diffusion report solely on structural dynamics. A small amount of very fast (~2 ps time scale) anisotropy decay is observed. The decay is concentration independent, and is assigned to wobbling-in-a-cone orientational motions of the RePhen(CO)3Cl. Theoretical calculations reported previously for experiments on a single concentration of the same type of sample suggested the presence of some vibrational excitation transfer and excitation transfer induced spectral diffusion. Possible reasons for the experimentally observed lack of excitation transfer in these high concentration samples are discussed.

show abstract

Section: Resultsmentioning

confidence: 99%

Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy

et al. 2012

View full text Add to dashboard Cite

show abstract

“…Prior to synthesizing the ditopic ligands ( L1 and L2 ; Scheme ), three model copper complexes were generated (Figure and the Supporting Information) to confirm that the different binding pockets would coordinate the relevant copper ions (Cu(I) for the bidentate ligands or Cu(II) for the tridentate ligand) in the expected manner. To synthesize the heteroleptic copper(I) complexes, 6,6′-dimesityl-2,2′-bipyridine (diMesbpy, 1 equiv) and [Cu(MeCN) 4 ](PF 6 ) (1 equiv) were combined in acetone to form the [Cu(MeCN) 2 (diMesbpy)](PF 6 ) intermediate. , Then, either 2-(1-benzyl-1 H -1,2,3-triazol-4-yl)pyridine (pytri) or 1-benzyl-4-(2,2′-bipyridin-5-yl)-1 H -1,2,3-triazole (bpytri) (1 equiv) was added to generate dark red solutions from which orange/red crystals could be obtained (Supporting Information). The heteroleptic Cu(II) complex was synthesized by stirring CuCl 2 (1 equiv) and AgPF 6 in acetone to extract the chloride ions and generate the solvated Cu(II) complex in solution.…”

Section: Results and Discussionmentioning

confidence: 99%

“…To synthesize the heteroleptic copper(I) complexes, 6,6′-dimesityl-2,2′-bipyridine (diMesbpy, 1 equiv) 72 and [Cu(MeCN) 4 ](PF 6 ) (1 equiv) were combined in acetone to form the [Cu(MeCN) 2 (diMesbpy)](PF 6 ) intermediate. 50,73 Then, either 2-(1-benzyl-1H-1,2,3-triazol-4yl)pyridine (pytri) 74 or 1-benzyl-4-(2,2′-bipyridin-5-yl)-1H-1,2,3-triazole (bpytri) 75 (1 equiv) was added to generate dark red solutions from which orange/red crystals could be obtained (Supporting Information). The heteroleptic Cu(II) complex was synthesized by stirring CuCl 2 (1 equiv) and AgPF 6 in acetone to extract the chloride ions and generate the solvated Cu(II) complex in solution.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Can 2-Pyridyl-1,2,3-triazole “Click” Ligands be Used to Develop Cu(I)/Cu(II) Molecular Switches?

et al. 2021

View full text Add to dashboard Cite

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.

show abstract

“…Benzyl-1H-1,2,3-triazol-4-yl) The compound characterization is in agreement with that previously reported. 31 Bis(1-benzyl-1H-1,2,3-triazol-4-yl) M ethoxyphenyl)-1-methyl-1H-1,2,3-triazole (2t Hexyl-4-(4-methoxyphenyl)-1H-1,2,3-triazole (2v) The solvent mixture used was MeOH-H 2 O-THF (1:1:1), at the same concentration as that indicated in the general procedure.…”

Section: Pyridine (2q)mentioning

confidence: 99%

One-Pot Click Synthesis of 1N-Alkyl-4-aryl-1,2,3-triazoles from Protected Arylalkynes and Alkyl Bromides

Ladouceur¹,

Soliman²,

Zysman‐Colman³

2011

Synthesis

View full text Add to dashboard Cite

1N-Alkyl-4-aryl-1,2,3-triazoles have been prepared through a multicomponent one-pot protocol from the corresponding (arylethynyl)trimethylsilanes and alkyl bromides. In situ alkyl azide formation and alkyne deprotection followed by copper(I)-catalyzed click cycloaddition afforded the desired 1,4-disubstituted 1,2,3-triazoles in generally good to excellent yield, with only minor observation of the undesired 1,5-regioisomeric cycloadduct. The protocol eliminates the need to use reactive organic azides and terminal alkynes.

show abstract

Rhenium tricarbonyl complexes of 1-benzyl-4-(5-bipyridyl)-1H-1,2,3-triazoles

Cited by 9 publications

References 38 publications

Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy

Dynamics of Functionalized Surface Molecular Monolayers Studied with Ultrafast Infrared Vibrational Spectroscopy

Can 2-Pyridyl-1,2,3-triazole “Click” Ligands be Used to Develop Cu(I)/Cu(II) Molecular Switches?

One-Pot Click Synthesis of 1N-Alkyl-4-aryl-1,2,3-triazoles from Protected Arylalkynes and Alkyl Bromides

Contact Info

Product

Resources

About