Cationic organoiron mixed-sandwich hydrazine complexes: Reactivity toward aldehydes, ketones, β-diketones and dioxomolybdenum complexes

Manzur, Carolina; Fuentealba, Mauricio; Hamon, Jean‐René; Carrillo, David

doi:10.1016/j.ccr.2009.11.001

Cited by 24 publications

(9 citation statements)

References 128 publications

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“…Ferrocenes such as the seminal example of cis ‐1‐ferrocenyl‐2‐(4‐nitrophenyl)ethylene (Figure , left) were found by Green's group, followed by other groups, to show nonlinear optical (NLO) properties, with applications in optical signal processing such as the frequency doubling of laser light.…”

Section: Ferrocenes In Supramolecular Ensembles Liquid Crystals Andmentioning

confidence: 99%

“…It turned out that both the reduction reactions and the organic connectors had a significant influence on the 4,4′‐bipyridinium system . The groups of Hamon, Saillard, Carrillo, Manzur, and Ledoux‐Rak developed another remarkable series of molecular systems in which ferrocene is conjugated with Schiff bases; excellent NLO properties were disclosed . The largest quadratic hyperpolarizability value (970 × 10 –30 esu) was determined for palladium‐containing dimetallic ferrocene Schiff‐base species .…”

Section: Ferrocenes In Supramolecular Ensembles Liquid Crystals Andmentioning

confidence: 99%

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Why is Ferrocene so Exceptional?

2016

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The appearance of ferrocene in the middle of the 20th century has revolutionized organometallic chemistry and is now providing applications in areas as varied and sometimes initially unexpected as optical and redox devices, battery and other materials, sensing, catalysis, including asymmetric and enantioselective catalysis, and medicine. The author presents here a general, although personal, view of ferrocene's chemistry, properties, functions, and applications through a literature survey involving both historical and up‐to‐date trends and including examples of his group's research in a number of these areas. The review gathers together general features of ferrocene chemistry and representative examples of the salient aspects. Its focus is on ferrocene's basic properties, ferrocene‐containing ligands, the ferrocene/ferricinium redox couple, ferrocene mixed‐valence and average‐valence systems, the ferricinium/ferrocene redox shuttle in catalysis, ligand‐exchange reactions, ferrocene‐containing polymers, ferrocene‐containing structures for cathodic battery and other materials, ferrocenes in supramolecular ensembles, liquid crystals, and nonlinear optical materials, ferrocene‐containing stars and their electrostatic effects, ferrocene‐containing dendrons, dendrimers, and nanoparticles (NPs) and their application in redox sensing and catalysis, and ferrocenes in nanomedicine.

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Section: Ferrocenes In Supramolecular Ensembles Liquid Crystals Andmentioning

confidence: 99%

Section: Ferrocenes In Supramolecular Ensembles Liquid Crystals Andmentioning

confidence: 99%

Why is Ferrocene so Exceptional?

2016

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“…Due to the potential utility in novel optoelectronic and photonic technologies, molecular materials with large nonlinear optical (NLO) properties are of great interest and have been extensively investigated both experimentally and theoretically . An increasing amount of research has shown that organometallic complexes of transition metals offer versatility for combining NLO effects with other characteristics, such as ultrafast response times, low dielectric constants, good processability as thin-film devices, and enhanced nonresonant responses in view of producing novel multifunctional materials . Besides, organometallic compounds also show advantages over traditional organic molecules owing to their strong UV/vis absorption bands (metal-to-ligand charge transfer and ligand-to-metal charge transfer), their redox properties, and the tuning effect of the metal on the electronic properties of the organic fragments .…”

Section: Introductionmentioning

confidence: 99%

Understanding the Second-Order Nonlinear Optical Properties of One-Dimensional Ruthenium(II) Ammine Complexes

Zhang

Champagne

2013

J. Phys. Chem. C

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First principles calculations of the linear and nonlinear optical properties are carried out for three series of one-dimensional ruthenium(II) ammine complexes with one pyridyl pyridinium ligand containing different numbers of C2H2 units or the (CHCH)Ph(CHCH) linker. The substitution effects upon introducing one pyridine or one N-methylimidazole moiety as donor instead of ammonia have also been studied in detail. These calculations employing density functional theory with different exchange-correlation functionals as well as the polarizable continuum model approach to describe the solvent effects show that these compounds are challenging for theoretical chemistry and that their nonlinear optical responses are complex and depend on many structural and electronic factors. Two major types of methods have been employed to calculate and analyze the first hyperpolarizabilities (β): (i) the summation-over-states scheme, applied to calculate the longitudinal β tensor component, truncated to one or two dominant excited states, of which the results are compared to Stark spectroscopy data, and (ii) the quadratic response schemes, providing the whole second harmonic generation response of the compound, which can be compared to the values derived from hyper-Rayleigh scattering measurements. Using response theory calculations, off-resonant first hyperpolarizability values display a monotonic increase as a function of the number of C2H2 units (from 0 to 3 units, corresponding to compounds 1–4, respectively) in the pyridyl pyridinium ligand (in the three series with NH3, pyridine, and N-methylimidazole substituent in opposite position to the large ligand). These calculations, which evidence the dominance of the longitudinal β tensor component and a consistent depolarization ratio close to 5.0, also predict a smaller β value when the (CHCH)3 linker of the pyridyl pyridinium ligand (compound 4) is replaced by the (CHCH)Ph(CHCH) linker (compound 5). To some extent, the calculations performed at a wavelength of 1064 nm confirm these trends, despite the presence of resonance enhancements. Calculations carried out within the summation-over-states scheme to analyze the origin of these β variations reproduce the monotonic increase of β in the 1–4 series, but compounds 4 and 5 are predicted to have similar β values. Upon relating these β variations to those of spectroscopic properties like the excitation energies, transition dipoles, and dipole moments of a pair of excited states (a low-energy metal to ligand charge transfer and a high-energy intraligand charge transfer excited state), the calculations point out the impact of including a second excited state in the treatment, since it leads to a decrease of β by about 50%. Though substituting the ammonia group by a pyridine has a limited impact on the linear and nonlinear optical properties of the complexes, the substitution by N-methylimidazole increases β by about 25%, which has been attributed to the contribution of N-methylimidazole to the HOMO and the subsequent batho...

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“…In the past decades, the nonlinear optical (NLO) materials based on molecular compounds are of considerable interest because they hold promise for applications in biological imaging, advanced optoelectronic and all-optical data processing technologies. − Among the NLO materials, although purely organic compounds have received much attention, organometallic complexes are especially interesting in this context. Because the organometallic complexes offer versatility for combining NLO effects with other characteristics, such as ultrafast response times, low dielectric constants, good processability as thin-film devices, and enhanced nonresonant responses in view of producing novel multifunctional materials. − Besides, organometallic complexes also show advantages over traditional organic molecules owing to their several low-energy metal-to-ligand charge transfer (MLCT), ligand-to-metal charge transfer (LMCT) or metal-to-metal/intervalence charge transfer (MM/IVCT) excitations, − redox properties, and the tuning effect of the metal on the electronic properties of the organic fragments. − Therefore, organometallic complexes have become the excellent NLO materials.…”

Section: Introductionmentioning

confidence: 99%

Strategy for Enhancing Second-Order Nonlinear Optical Properties of the Pt(II) Dithienylethene Complexes: Substituent Effect, π-Conjugated Influence, and Photoisomerization Switch

Zhang

Wang

et al. 2013

J. Phys. Chem. A

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The second-order nonlinear optical (NLO) properties of a series of Pt(II) dithienylethene (DTE) complexes possessing the reversible photochromic behavior have been investigated by density functional theory (DFT) combined with the analytic derivatives method. The results show that the calculated static first hyperpolarizabilities (βtot) of the open-ring and closed-ring systems significantly increase in the range of 2.1-4.5 times through strengthening of the electron-withdrawing ability of the substituent R (R = H, CF3, NO2) and an increase of the number of thiophene rings. Moreover, there is a large enhancement of the βtot values from the open-ring systems to the corresponding closed-ring systems. This efficient enhancement is attributed to the better delocalization of the π-electron system, the more obvious degree of charge transfer, and the larger f(os)/E(gm)(3) (f(os) is the oscillator strength, and E(gm) is the transition energy between the ground and the excited states) values in the closed forms according to the bond length alternation (BLA) and time-dependent density functional theory (TDDFT) calculations. In addition, the dispersion has less influence on the frequency-dependent first hyperpolarizabilities (βtot(ω)) of the studied systems at the low-frequency area ω (0.000-0.040 au). Our present work would be beneficial for further theoretical and experimental studies on large second-order NLO responses of metal complexes.

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Cationic organoiron mixed-sandwich hydrazine complexes: Reactivity toward aldehydes, ketones, β-diketones and dioxomolybdenum complexes

Cited by 24 publications

References 128 publications

Why is Ferrocene so Exceptional?

Why is Ferrocene so Exceptional?

Understanding the Second-Order Nonlinear Optical Properties of One-Dimensional Ruthenium(II) Ammine Complexes

Strategy for Enhancing Second-Order Nonlinear Optical Properties of the Pt(II) Dithienylethene Complexes: Substituent Effect, π-Conjugated Influence, and Photoisomerization Switch

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