A study of the effect of pyridine linkers on the viscosity and electrochromic properties of metallo-supramolecular coordination polymers

Pai, Sandesh; Schott, Marco; Niklaus, Lukas; Posset, Uwe; Kurth, Dirk G.

doi:10.1039/c7tc04177b

Cited by 55 publications

(33 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In addition, the coordination geometry of the bis terpyridine complex allows the design of linear arrays or polymers, [12][13][14] whose properties can be tuned by using different spacers as well as substituents. [15][16][17] Despite intensive efforts dedicated to improving their photophysical properties, ruthenium bis tridentate complexes have, to the best of our knowledge, not been shown to photocatalyze hydrogen production. 18,19 Herein, we report a newly designed heteroleptic complex capable of coordinating to the catalyst via peripheral pyridine substituents and discuss its photophysical and electrochemical properties as well as its potential as photosensitizer in hydrogen production experiments.…”

Section: Introductionmentioning

confidence: 99%

Photocatalytic Hydrogen Evolution Driven by a Heteroleptic Ruthenium(II) Bis(terpyridine) Complex

et al. 2019

Self Cite

View full text Add to dashboard Cite

Since the initial report by Lehn et al. in 1979, ruthenium tris(bipyridine) ([Ru(bpy) 3 ] 2+ ) and its numerous derivatives were applied as photosensitizers (PSs) in a large panel of photocatalytic conditions while the bis(terpyridine) analogues were disregarded because of their low quantum yields and short excited-state lifetimes. In this study, we prepared a new terpyridine ligand, 4′-(4-bromophenyl)-4,4‴:4″,4‴′-dipyridinyl-2,2′:6′,2″-terpyridine (Bipytpy) and used it to prepare the heteroleptic complex [Ru(Tolyltpy)(Bipytpy)](PF 6 ) 2 (1; Tolyltpy = 4′tolyl-2,2′:6′,2′-terpyridine). Complex 1 exhibits enhanced photophysical properties with a higher quantum yield (7.4 × 10 -4 ) and a longer excited-state lifetime (3.8 ns) compared to those of [Ru(Tolyltpy) 2 ](PF 6 ) 2 (3 × 10 -5 and 0.74 ns, respectively). These enhanced photophysical characteristics and the potential for PS-catalyst interaction through the peripheral pyridines led us to apply the complex for visible-light-driven hydrogen evolution.The photocatalytic system based on 1 as the PS, triethanolamine as a sacrificial donor, and cobaloxime as a catalyst exhibits sustained activity over more than 10 days under blue-light irradiation (light-emitting diode centered at 450 nm). A maximum turnover number of 764 was obtained after 12 days.

show abstract

Section: Introductionmentioning

confidence: 99%

Photocatalytic Hydrogen Evolution Driven by a Heteroleptic Ruthenium(II) Bis(terpyridine) Complex

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Iron(II) terpyridine complexes are classical examples of coordination compounds exhibiting a typical (terimine)iron(II) chromophore in a low spin configuration. [1][2][3] The complexes have been extensively employed in analytical chemistry, coordination polymers 4 and devices 5 because of their strong red-violet colors associated with metal-to-ligand charge-transfer transitions in the visible region. However, the analogous iron(II) terpyrazine complexes remain poorly understood, and according to the best of our knowledge, they have never been investigated before from the point of view of their electronic, Raman and supramolecular properties in aqueous solution.…”

Section: Introductionmentioning

confidence: 99%

Raman Studies of Bis(phenylterpyrazine)iron(ii) and Supramolecular Species With Pentacyanidoferrate(ii) Ions

Mangoni¹,

Brandão²,

Shinohara³

et al. 2019

Quím. Nova

View full text Add to dashboard Cite

The chemistry and spectroscopy of the iron(II) phenylterpyrazine complex, [Fe(phtpz) 2 ] 2+ , were investigated in comparison with the analogous phenylterpyridine species, Fe(phtpy) 2 ] 2+ , and the results indicated a strong electronic delocalization on the Fe(II) terimine chromophore encompassing the lateral pyrazyl groups. The delocalized nature of the molecular orbitals involved in the electronic excitation precluded a direct assignment of the pyridine and pyrazine vibrations in the complex. However, the capability of the terpyrazine complex to bind transition metal ions, such as the [Fe(CN) 5 ] 3species, allowed to generate pentanuclear complexes displaying characteristic charge-transfer and resonance Raman spectra, revealing the pyrazine vibrations in the complex. The [Fe(CN) 5 ] 3containing species also yielded polymeric compounds in presence of transition metal ions, exhibiting intervalence transfer bands and chemical similarities with the Prussian Blue complex.

show abstract

“…Furthermore, the use of two different electrochromic layers would afford devices with new optical properties that cannot be obtained with monomolecular films. Several classes of electrochromic materials have been developed, ranging from transition metal oxides, polymers, and small organic molecules, to coordination complexes . For example, Hammond et al.…”

Section: Figurementioning

confidence: 99%

Bifunctional Nanoscale Assemblies: Multistate Electrochromics Coupled with Charge Trapping and Release

2020

View full text Add to dashboard Cite

We demonstrate controlled charge trapping and release,a ccompanied by multiple color changes in am etalloorganic bilayer.T he dual functionality of the metallo-organic materials provides fundamental insight into the metal-mediated electron transport pathways. The electrochemical processes are visualizedb yd istinct, four color-to-color transitions: red, transparent, orange,and brown. The bilayer is composed of two elements:1 )a nanoscale gate consisting of al ayer of well-defined polypyridyl ruthenium complexes bound to af lexible transparent electrode,a nd 2) ac harge storage layer consisting of isostructural iron complexes attached to the surface of the gate.T his gate mediates or blocks electron transport in response to an applied voltage.The charge storage and release depend on the oxidation state of the layer of ruthenium complexes (= gate). Combining electrochemistry with optical data revealed mechanistic information:the brown coloration of the bilayer directly relates to the formation of intermediate ruthenium species,p roviding evidence for catalytic positive charge release mediated through the gate.[*] Y. Hamo, Dr.M.L ahav,P rof. M. E. van der Boom

show abstract

A study of the effect of pyridine linkers on the viscosity and electrochromic properties of metallo-supramolecular coordination polymers

Abstract: We present the optical, electrochemical, and electrochromic properties of Fe(ii)-, Co(ii)- and Ru(ii)-based metallo-supramolecular polymers (MEPEs) self-assembled from rigid, π-conjugated bis-terpyridines with different numbers of pyridine linkers.

Cited by 55 publications

References 55 publications

Photocatalytic Hydrogen Evolution Driven by a Heteroleptic Ruthenium(II) Bis(terpyridine) Complex

Photocatalytic Hydrogen Evolution Driven by a Heteroleptic Ruthenium(II) Bis(terpyridine) Complex

Raman Studies of Bis(phenylterpyrazine)iron(ii) and Supramolecular Species With Pentacyanidoferrate(ii) Ions

Bifunctional Nanoscale Assemblies: Multistate Electrochromics Coupled with Charge Trapping and Release

Contact Info

Product

Resources

About