The known complex {Cp(PPh3)2Ru}2(μ-C⋮CC⋮C) (3-Ph) and its PMe3-substitution product {Cp(PPh3)(PMe3)Ru}2(μ-C⋮CC⋮C) (3-Me) have been shown by cyclic voltammetry to undergo a series of four stepwise one-electron oxidation processes. Successive potentials (V) for the first three reversible processes 3-Ph are −0.23 (−0.26), +0.41 (+0.33), +1.03 (+0.97); fourth, irreversible at +1.68 (+1.46) V is accompanied chemical transformation followed further oxidation. Chemical with 1 or 2.5 equiv AgPF6 in...

In this Perspective, we highlight the non-innocent behaviour of bridging ligand in organometallic polynuclear metallic complexes displaying metal-carbon σ bonds between units and a strongly coupled conjugated carbon-rich ligand. With help representative experimental theoretical studies on polymetallic systems, but also monometallic complexes, point out that level implication carbon rich redox processes is very sensitive to nature (i) metal(s), (ii) ancillary ligands (iii) itself,...

A thermally activated delayed fluorescence (TADF) tetrametallic Cu(I) metallacycle behaves as a conformationally adaptive preorganized precursor to afford, through straightforward and rational coordination-driven supramolecular processes, variety of room-temperature solid-state luminescent polymetallic assemblies. Reacting various cyano-based building blocks with A, homometallic 1D-helical coordination polymer C Cu8M discrete circular heterobimetallic assemblies DM (M = Ni, Pd, Pt) are...

This study reports the isolation and structural (X-ray), UV−vis, NMR characterization of a series electron-rich Ru(II) acetylide complexes formula (η2-dppe)(η5-C5Me5)Ru(C⋮C)-1,4-(C6H4)X (1a−f; X = NO2, CN, F, H, OMe, NH2) (η2-dppe)(η5-C5Me5)Ru(C⋮C)-1,3-(C6H4)F (1c-m), as well spectroscopic (near-IR ESR) in situ corresponding elusive Ru(III) radical cations. The data are discussed connection with DFT computations, consistent picture electronic structure these is proposed. Notably, strong...

We describe how the association between an ytterbium ion and a ruthenium carbon-rich complex enables first switching of near-IR Yb(III) luminescence by taking advantage redox commutation antenna.

Photo-modulable molecular transport junctions are developed via on-wire lithography-fabricated nanogaps functionalized with a dithienylethene unit bearing two ruthenium fragments. A reversible and repeatable bi-state conductive switching upon alternate irradiation of UV visible light can be distinctly observed. Theoretical calculations further suggest that bi-directional isomerization is due to the moieties modulate judiciously electronic coupling between photochromic part metal electrodes,...

Reactions in water of 4,5-dichlorophthalate (dcpa2–) with the heaviest lanthanide ions lead to a family compounds general chemical formula [Ln2(dcpa)3(H2O)5·3H2O]∞, where Ln = Tb–Lu, Y. The synthesis, crystal structure, thermal behavior, and luminescent properties this series homonuclear are described. Additionally, can be extended isostructural heteronuclear that contain some light therefore present original photophysical properties. These show potential interest as multiemissive materials...

The straightforward synthesis of a new Cu(i) metal-rich small metallacycle is presented. This compound luminescent in the solid state with an emission quantum yield 72% at room temperature and displays pronounced reversible red-shift its spectra upon cooling. Quantum chemical calculations reveal that these properties are governed by important geometrical relaxations imply formation cuprophilic interactions excited states.

The bi- and trinuclear iron(III) complexes [1,3-{Cp*(dppe)Fe(C⋮C−)}2(C6H4)][PF6]2 (22+) [1,3,5-{Cp*(dppe)Fe(C⋮C−)}3(C6H3)] [PF6] (33+) were prepared by oxidation of [1,3-{Cp*(dppe)Fe(C⋮C−)}2(C6H4)] or with 2 3 equiv [(C5H5)2Fe][PF6], respectively. Complexes 22+ 33+ isolated as thermally air stable blue microcrystalline solids in 95 80% yield, These paramagnetic compounds characterized cyclic voltammetry, IR, UV−vis, 1H NMR, Mössbauer, ESR spectroscopies. three organoiron groups are not...

The synthesis, photophysical and nonlinear optical properties of several new multi-octupolar tris(bipyridine) ruthenium complexes are reported. preparation on these is based the initial construction multipodal 4,4'-dialkylaminostyryl-2,2'-bipyridine ligands (DAAS-bpy). Thermally stable polyimides featuring octupolar trisbipyridyl have been readily obtained by a polycondensation reaction. controlled coordination strategy dipodal tripodal bipyridines to ruthenium(II) has also successfully used...

A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C)Fe(C(5)Me(5))(dppe)], 1, and its oxidized species, bond]C)Fe(C(5)Me(5))(dppe)][PF(6)], 2, have been synthesized their X-ray crystal structures determined. related vinylidene bond]C[bond]C(6)H(4)[bond](H)C[double 3, has also characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at -1.49 V (vs SCE), fully reversible oxidation -0.19 V, +0.88 V. In...

The reactions of FeCl(dppe)Cp* and Ru(C⋮CC⋮CH)L2Cp' with Na[BPh4] 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu; 2 equiv) in a mixed thf/NEt3 solvent afford {Cp*(dppe)Fe}(C⋮CC⋮C){Ru(PP)Cp'} (PP = dppe, Cp' Cp*, 7; PP (PPh3)2, Cp, 8). Cyclic voltammetry shows that these Fe/Ru complexes undergo sequential loss up to three electrons, the mono- dioxidized species being isolated following chemical oxidation. Computational (DFT) spectroscopic (IR, NMR, ESR, Mössbauer) studies are consistent polarized...

The present study reports the isolation and structural (X-ray), UV−vis−near-IR, ESR characterization of a series Fe(III) complexes formula [(η2-dppe)(η5-C5Me5)Fe(C⋮CC6H4X)][PF6] (1a[PF6]−1k[PF6]; with X = NO2, CN, CF3, Br, F, H, Me, tBu, OMe, NH2, NMe2). electronic substituent effect remote group on structure is experimentally evidenced by means correlations parameters (ESPs) theoretically investigated. spectroscopic data are discussed in connection DFT computations. A consistent picture...

A novel bis(iron) alkynyl-bridged complex, Cp*(dppe)Fe(C⋮C-9,10-ant-C⋮C)Fe(dppe)Cp*, 10 (ant = anthracene), and its oxidized forms, 10·PF6, 10·TCNQ, 10·2PF6, were synthesized characterized by X-ray crystal structures. The cyclic voltammogram of shows two well-reversible redox couples at −0.40 −0.04 V (vs SCE) a third process close to the solvent edge. Density-functional theory (DFT) calculations carried out on substituted model complex...

Density functional theory has been used to probe the bonding and electronic properties of homo- heterobimetallic sp carbon chain complexes (ML(m), = (eta(5)-C(5)R(5))(eta(2)-R(2)PCH(2)CH(2)PR(2))Fe, (eta(5)-C(5)R(5))(NO)(PR(3))Re; z 0-4). All neutral are best described by MCtbd1;CCtbd1;CM structures, in accord with much experimental data. The singlet dications cumulenic (+)M=C=C=C=C=M(+) valence formulations. However, diiron rhenium/iron found possess triplet states nearly identical energy,...

μ·β products were experimentally derived by EFISH for several Fe(II) and Fe(III) σ-aryl acetylides of formula [(η2-dppe)(η5-C5Me5)Fe(C⋮C−Ar)]n+, n(PF6) - (dppe = 1,2-bis(diphenylphosphino)ethane; n 0, 1), where Ar p-Py, m-Py, o-Py (1a−c/1a+); p-C5H4-N(CH3)+, o-C5H4-N(CH3)+ (2a,b+); p-C6H4X with X NO2, CN, CF3, H, OMe, NH2 (3a−f/3a−f +). For comparison purposes, data also gathered on the Ru(II) analogues (4a,b) 3a,b. Significant figures determined, complexes 2a+ 3a,b possessing most...

Two methodologies of C-C bond formation to achieve organometallic complexes with 7 or 9 conjugated carbon atoms are described. A C7 annelated trans-[Cl(dppe)2Ru=C=C=C-CH=C(CH2)-C[triple bond]C-Ru(dppe)2Cl][X] (X = PF6, OTf) complex is obtained from the diyne trans-[Cl(dppe)2Ru-(C[triple bond]C)2-R] (R H, SiMe3) in presence [FeCp2][PF6] HOTf, and C9 bond]C)n-C(CH3)=C(R1)-C(R2)=C=C=Ru(dppe)2Cl][X] (n 1, 2; R1 Me, Ph, R2 Me; X BF4, formed a polyyne bond]C)n-R] 2, 3; R ruthenium allenylidene...

The electronic structures of the electron-rich Fe(II) acetylide complexes (η2-dppe)(η5-C5Me5)Fe(C⋮CC6H4-X) (1a−j: dppe = 1,2-bis(diphenylphosphino)ethane; X NO2, CN, CF3, Br, F, H, Me, tBu, OMe, NH2) have been investigated using density functional theory calculations. crystal bromo- (1d), methyl- (1g), methoxy- (1i), and amino-substituted (1j) are reported to complement available structural data. data, first ionization potentials, relevant vibronic transitions calculated for model compared...

The perturbation of a dithienylethene system by ruthenium carbon-rich system, and vice versa, was used to reach unique sophisticated light- electro-triggered multifunctional switch featuring multicolor electrochromism, electrocyclization at remarkably low voltage, photo/electro tuning electronic communication.

In this work, we report the synthesis and electronic properties of unique highly conjugated molecular wires trans-[Cl−(dppe)2Ru═C═C═(Ph)C−CH═(CH3)C−C≡C−(X)2Ru−C≡C−C(CH3)═CH−C(Ph)═C═C═Ru(dppe)2Cl]n+ (n = 2, X dppe ([3a](OTf)2) dppm ([3b](OTf)2) with three similar metal centers spanned by two odd-numbered unsaturated C7 chains providing a 28 Å long path displaying five well-separated redox states 0−4). Successive one-electron transfer steps were studied means cyclic voltammetry, EPR...

The role of the nitrogen atom on electronic and magnetic couplings mono-oxidized bi-oxidized pyridine-containing complex models [2,6-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) [3,5-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) is theoretically tackled with aid density-functional theory (DFT) multireference configuration interaction (MR-CI) calculations. Results are analyzed compared to those obtained for reference [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+). species show an interesting behavior at borderline...

Abstract The new [(η 2 ‐dppe)(η 5 ‐C Me )Fe(CC‐1,4‐C 6 H 4 CC)Ru(η ‐dppe) CC(C )] complex ( 3‐H ) and its hexanuclear relative [{(η ‐CC)Ru(η (CC‐1,4‐C CC) 3 (1,3,5‐C have been synthesized characterized. linear cubic nonlinear optical properties of these compounds in their various redox states studied along with those the analogous complexes R][PF ] n =0–2; R=Cl, 2‐Cl ; R=CC(4‐C NO ), 3‐NO ). We show that molecules exhibiting large third‐order nonlinearities can be obtained by...

The combined time-resolved photoluminescence (PL) and theoretical study performed on luminescent [Mo6Br(i)8Br(a)6](2-)-based systems unambiguously shows that their NIR-luminescence is due to at least two emissive states. By quantum chemical studies, we show for the first time important geometrical relaxations occur triplet states either by outstretching of an apex away from square plane Mo6 octahedron or elongation one Mo-Mo bond. Experimental PL measurements demonstrate external environment...

A central issue in molecular electronics order to build functional devices is assess whether changes the electronic structure of isolated compounds by chemical derivatization are retained once molecules inserted into junctions. Recent theoretical studies have suggested that this not always case due occurrence pinning effects making alignment transporting levels insensitive systems. We explore here phenomenon investigating at both experimental and I/V characteristics junctions incorporating...

The bi- and trinuclear mixed-valence complexes [{Cp*(dppe)Fe(CC−)}2(1,3-C6H4)][PF6] (2+), [{Cp*(dppe)Fe(CC−)}3(1,3,5-C6H3)][PF6] (3+), [{Cp*(dppe)Fe(CC−)}3(1,3,5-C6H3)][PF6]2 (32+) were prepared either by oxidation of [{Cp*(dppe)Fe(CC−)}2(1,3-C6H4)] (2) or [{Cp*(dppe)Fe(CC−)}3(1,3,5-C6H3)] (3) with 1 2 equiv [(C5H5)2Fe][PF6] reaction between the homovalent species 22+ 3 33+. After crystallization (CH2Cl2/pentane) at −20 °C, 2+, 3+, 32+ isolated in good yields (80−93%). well-resolved...