Keggin and Dawson-type polyoxometalates (POMs) decorated by organometallic [cyclometalated ruthenium(II) polypyridine complex] or organic (pyrene) chromophores were prepared postfunctionalization of hybrid disilylated POM platforms. The connection is made in a very efficient modular way via Sonogashira coupling reactions, which provide rigid linkage between the photoactive centers. Electronic properties have been inferred from electrochemical photophysical studies reflect poor electronic...

Abstract Transition metals are extremely useful tools for the preparation of rotaxanes and catenanes. Traditionally, copper( I ) has played an important role in this field, but recently octahedrally coordinated metal centres such as ruthenium( II ), have allowed highly functional interlocking ring systems. The present review article will discuss new approach, which gives access to novel Besides purely synthetic work described, potential prepared compounds be used light‐driven molecular...

Novel NCN-pincer carbene complexes of Ru(II), 1,3-bis(2-pyridylmethyl)benzimidazolineruthenium(II) bishexafluorophosphate (2), and Pt(II), 1,3-bis(2-pyridylmethyl)benzimidazolinechloroplatinum(II) hexafluorophosphate (3), based on 1,3-bis(2-pyridylmethyl)-1H-benzimidazolium chloride (1) were synthesized characterized by different spectroscopic methods. Complex 2 shows an absorption maximum at 386 nm, blue-shifted in comparison to Ru(bpy)32+ Ru(tpy)22+, probably due the strong σ-donor weak...

This work describes the synthesis and characterization of two new bis-terdentate Ru(II) complexes. Compound 1 is a homoleptic complex containing CNC N-heterocyclic carbene (NHC) based ligands, whereas compound 2 bears one ligand an ancillary terpyridine ligand. The redox photophysical properties both compounds have been investigated their X-ray crystal structures determined. Complex displays close-to-perfect octahedral coordination geometry not luminescent at room temperature while features...

Dioxygen activation by copper complexes is a valuable method to achieve oxidation reactions for sustainable chemistry. The development of catalytic system requires regeneration the Cu(I) active redox state from Cu(II). This usually achieved using extra reducers that can compete with Cu(II)(O2) oxidizing species, causing loss efficiency. An alternative would consist photosensitizer control reduction process. Association Ru(II) photosensitizing subunit Cu(II) pre-catalytic moiety assembled...

Photochromic coordination polymers, based on zinc(<sc>ii</sc>) bis-terpyridine-appended dimethyldihydropyrene building blocks, have been synthesized following stepwise synthesis a surface yielding photo-switchable molecular junctions.

Three new ruthenium(II) complexes have been prepared which contain two 1,10-phenanthroline units and a third sterically hindering chelate. In one case, the ligand is disubstituted 2,2'-bipyridine (bpy) attached to very bulky manisyl groups. The other systems are similar in terms of size groups (anisyl substituents) located close central metal. investigated Present Report aimed at providing building blocks future light-driven molecular machines. photochemical expulsion chelate has thus...

A rotaxane containing a ruthenium bisphenanthroline complex, acting as an axis, and macrocycle incorporating 2,2'-bipyridine (bpy) unit, threaded by the has been synthesized. The ligand is such that its ruthenium(II) complexes possess clearly identified making compounds ideal components of rotaxanes constructed around octahedral center, which serves template. ring axial precursor to afford corresponding pseudorotaxane in moderate yield. X-ray structure analysis this compound reveals nature...

The synthesis of two multisite ligands containing four and five 1,10-phenanthroline (phen) chelates in line, respectively, is presented. connectors are 1,3-phenylene linkers. were prepared following multistep procedures, the key reactions being Suzuki coupling reaction between aromatic nuclei nucleophilic addition aryllithium derivatives onto a phen fragment. coordination chemistry both with Li+ ions was very clean selective, whereas their copper(I) led to intractable mixtures insoluble...

Abstract By incorporating a 6,6'‐diphenyl‐2,2'‐bipyridine (dpbipy) fragment in ring, endo coordination of ruthenium( II ) center is performed selectively and almost quantitatively. The threaded system, containing helical fragment, could be fully characterized. When the terminal functions rod‐shaped complex through macrocycle are phenol groups, complete rotaxane prepared by classical Williamson stoppering reaction moderate yield. Light‐induced motions unstoppered system (pseudorotaxane) real...

A new method based on the electrochemical oxidation of thiols was used to easily generate multilayer assemblies coordination complexes a gold surface. For this purpose, two bearing anchoring groups for surface attachment have been prepared: [Ru(tpySH)(2)](2+) (1) and [Fe(tpySH)(2)](2+) (2) (tpySH = 4'-(2-(p-phenoxy)ethanethiol)-2,2':6',2″-terpyridine). Cyclic voltammetry 1 in CH(3)CN exhibits successive processes. The first is irreversible attributed thiol substituents, whereas second...

A [Ru(bpy)3]2+-like complex (L1) bearing two free terpyridine groups at the 5 and 5′ positions of same bipyridine, linked by rigid linear 2,5-dimethyl phenylene bridges has been synthesized to open access classes molecular wires with photosensitive properties: a bimetallic coordination polymer an inorganic triad. In this Research Article, we report on synthesis characterization resulting [{RuII_FeII}n]4n+ alternated [CoIII_RuII_FeII]7+ triad based building block L1. The is fully...

Switchable compounds have been often described as promising candidates for electronic applications such molecular-scale calculators. A step further is the combination of several different switchable molecules in larger functional macromolecules to design more sophisticated Boolean logic gates. Here, complex devices built via a redox- and photoactive metallopolymer based on dithienylethene-appended iron bis-terpyridine units. The commutation individual building blocks achieved using light or...

The synthesis, photophysical properties, and structural characterization of a photodimerizable ditopic ligand are described. Upon irradiation at 366 nm, 1 dimerizes to the head-to-tail tetra-bpy 2. This thermally stable photodimer can be dissociated back using higher energy (254 nm).

The electrochemical control of the isomerization process a photo switchable dimethyldihydropyrene (DHP) derivative has been investigated.

Molecular systems and devices whose properties can be modulated using light as an external stimulus are the subject of numerous research studies in fields materials life sciences. In this context, use photochromic compounds that reversibly switch upon irradiation is particularly attractive. However, for many envisioned applications, particular biological purposes, illumination with harmful UV must avoided these photoactivable operate aqueous media. we have designed a benzo[e]-fused...

Under visible light irradiation <bold>[Cr(ttpy)2]3+</bold> can be reduced twice by a tertiary amine; the photoreduction processes are accelerated in presence of [Ru(bpy)₃]²⁺ acting as an antenna thanks to efficient electron transfer reaction from [Ru(bpy)₃]^2+* [Cr(ttpy)₂]³⁺.

Abstract Dioxygen activation by copper complexes is a valuable method to achieve oxidation reactions for sustainable chemistry. The development of catalytic system requires regeneration the Cu I active redox state from II . This usually achieved using extra reducers that can compete with (O 2 ) oxidizing species, causing loss efficiency. An alternative would consist photosensitizer control reduction process. Association Ru photosensitizing subunit pre‐catalytic moiety assembled within unique...

A new tridentate ligand based on acridine has been synthetized. The central heterocycle bears two pyridine coordinating units at positions 4 and 5. terdentate 2,7-di-tert-butyl-4,5-di(pyridin-2-yl)acridine (dtdpa) was then coordinated to a ruthenium(II) cation. corresponding homoleptic complex could only be obtained where both ligands coordinate the ruthenium in fac fashion. Thus, heteroleptic compound (2) constructed combination with terpyridine order constrain adopt mer geometry. Such...

A tri-metallic triad based on a [Ru(bpy)3](2+) moiety connected to Fe(ii) and Co(iii) bisterpyridine has been grafted an ITO electrode by stepwise procedure. Under visible light, in the presence of sacrificial electron donor, system produces electric current. The photo-current magnitude is compared one generated from Co(iii)-Ru(ii) dyad shows increase 40%.

Quantitative oxidation of [Fe(ttpy)2]2+ (1) (ttpy = 4′-(4-methylphenyl)-2,2′:6′,2″-terpyridine) has been performed in CH3CN by continuous photolysis experiments the presence [Ru(ttpy)2]2+ (2) and a large excess diazonium salt (ArN2+) as sacrificial oxidant. The reaction occurs with low quantum yield (ϕ 10–3). photooxidation process is fully characterized shows that acts an antenna transfers excitation energy to (1). latter complex its excited state oxidized ArN2+. Thiolated derivatives both...