Group 8 metal alkynyl complexes for nonlinear optics

International audienceStudies of the nonlinear optical (NLO) properties of Group 8 metal alkynyl complexes are summarized, with particular focus on results since 2003; structure-NLO property relationships are developed, optical nonlinearities of multipolar alkynyl complexes are described, and switching of the NLO response of molecules and molecular materials derived from Group 8 metal alkynyl complexes is discussed

Transition metal complex/gold nanoparticle hybrid materials

Gold nanoparticles (AuNPs) are of considerable interest for diverse applications in areas such as medicine, catalysis, and sensing. AuNPs are generally surface-stabilized by organic matrices and coatings, and while the resultant organic compound (OC)/AuNP hybrids have been explored extensively, they are not suitable for certain applications (e.g. those necessitating reversible redox behaviour and/or long excited-state lifetimes), and they often suffer from low photo- and/or thermal stability. Transition metal complex (TMC)/AuNP hybrids have recently come to the fore as they circumvent some of the aforementioned shortcomings with OC/AuNP hybrids. This review summarizes progress thus far in the nascent field of TMC/AuNP hybrids. The structure and composition of extant TMC/AuNP hybrids are briefly reviewed and the range of TMCs employed in the shell of the hybrids are summarized, the onephase, two-phase, and post-nanoparticle-synthesis synthetic methods to TMC/AuNP hybrids are discussed and contrasted, highlighting the advantages of variants of the last-mentioned procedure, and the utility of the various characterization techniques is discussed, emphasizing the need to employ multiple techniques in concert. Applications of TMC/AuNP hybrids in luminescence, electrochemical, and electro-optical sensing are described and critiqued, and their uses and potential in imaging, photodynamic therapy, nonlinear optics, and catalysis are assessed.We thank the Australian Research Council for support of this work (grant no. DP170100408). C.Q. thanks Becas Chile (CONICYT) for financial support in the form of a PhD scholarshi

Dynamic Permutational Isomerism in a closo-Cluster

Permutational isomers of trigonal bipyramidal [W2RhIr2(CO)9(η(5)-C5H5)2(η(5)-C5HMe4)] result from competitive capping of either a W2Ir or a WIr2 face of the tetrahedral cluster [W2Ir2(CO)10(η(5)-C5 H5)2] from its reaction with [Rh(CO)2(η(5)-C5HMe4)]. The permutational isomers slowly interconvert in solution by a cluster metal vertex exchange that is proposed to proceed by Rh-Ir and Rh-W bond cleavage and reformation, and via the intermediacy of an edge-bridged tetrahedral transition state. The permutational isomers display differing chemical and physical properties: replacement of CO by PPh3 occurs at one permutational isomer only, while the isomers display distinct optical power limiting behavior.We thank the Australian Research Council (Discovery Grant to M.G.H. and M.P.C., ARC Australian Research Fellowship to M.P.C.) for financial support. J.F. was the recipient of a China Scholarship Council ANU Postgraduate Scholarship

A Zinc(II) Tetraphenylporphyrin Peripherally Functionalized with Redox-Active "trans-[(η5-C5H5)Fe(η5-C5H4)C≡C](κ2- dppe)2Ru(C≡C)-" Substituents: Linear Electrochromism and Third-Order Nonlinear Optics

Dedicated to Dr. Claude Lapinte on the occasion of his retirement, in memory of the good times spent together in France and Australia.International audienceA nonametallic organometallic-coordination complex (4), assembled from redox-active ferrocenyl (Fc) and Ru(κ2-dppe)2 fragments (dppe = 1,2-bis(diphenylphosphino)ethane) as peripheral donor groups and a central Zn(II) tetraphenylporphyrin (ZnTPP) core, has been prepared and characterized. Complex 4 is obtained in one step from a pentametallic organometallic porphyrin precursor following substitution of the peripheral chloride ligands by ferrocenylalkynyl moieties (Ctriple bond; length of mdashCFc). The spectroelectrochemistry of 4, and that of previously reported porphyrins featuring related peripheral electron-rich d6-transition metal alkynyl units, has been investigated; the optical and redox properties of 4 are briefly discussed, and its potential, and that of a related pentanuclear tetraferrocenyl ZnTPP complex, to function as redox-switchable chromophores is examined. Preliminary studies of the cubic NLO properties of 4 have been undertaken by Z-scan studies at 560 nm and 630 nm, the results from which are also reported

Syntheses of Ir 4 (CO) 6 (η 5 -C 5 Me 4 H) 2 and Ir 7 (μ 3 -CO) 3 (CO) 12 (η 5 -C 5 Me 5 ) from Pentametallic Molybdenum-Iridium Cluster Precursors.

Reaction of Mo2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-C5Me5) with Ir(CO)2(η5-C5Me4H) afforded the four-valence-electron-deficien

Optical limiting properties of (reduced) graphene oxide covalently functionalized by coordination complexes

The nonlinear optical (NLO) and optical limiting (OL) properties of graphene oxide (GO), reduced graphene oxide (RGO), and particularly GO/RGO coordination complex hybrids are reviewed. A brief introduction to mechanisms of OL and a summary of the key measurement techniques for determining NLO/OL merit is provided. A summary of synthetic procedures to GO/RGO coordination complex hybrids is included.We thank the Australian Research Council (ARC) for financial support. D.M.A.S.D. was the recipient of an Australian Postgraduate Award

Facile hydrothermal synthesis and optical limiting properties of TiO 2 -reduced graphene oxide nanocomposites

TiO2/reduced graphene oxide (RGO) nanocomposites Gx (RGO titania nanocomposite, x grams tetrabutyl titanate per 0.03 g RGO, x = 0.25, 0.50, 1.00) were prepared by a hydrothermal method: graphene oxide was reduced to RGO in a 2:1 water:ethanol mixture in the presence of varying quantities of tetrabutyl titanate, which deposited as TiO2 on the RGO sheets. The nanocomposites were characterized by a combination of Fourier transform infrared spectroscopy, diffuse reflectance ultraviolet-visible spectroscopy, photoluminescence spectroscopy, Raman spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy studies. The nanocomposite G0.25 exhibits enhanced nonlinear optical properties compared to its individual components, which is ascribed to a combination of mechanisms. The role of defects and electron/energy transfer in the optical limiting performance of G0.25 was clarified with the help of Raman and photoluminescence spectroscopies. Intensity-dependent switching between reverse saturable absorption and saturable absorption behavior was observed with the G0.50 nanocomposite

Enhanced two-photon absorption cross-sections of zinc(II) tetraphenylporphyrins peripherally substituted with d(6)-metal alkynyl complexes

International audienceThe syntheses of new Zn(II) tetraphenylporphyrin (ZnTPP) derivatives functionalized with electron-rich d6-transition metal alkynyl complexes at their periphery are reported. Z-scan measurements reveal remarkably large effective two-photon absorption (TPA) cross-sections in the visible range for these compounds

Exceptionally large two- and three-photon absorption cross-sections by OPV organometalation

Oligo(p-phenylenevinylene)s (OPVs) containing up to 8 PV units and end-functionalized by ruthenium alkynyl groups have been prepared and their nonlinear absorption properties assessed using the Z-scan technique and employing low repetition rate femtosecond pulses. Exceptionally large two-photon absorption (ca. 12 500 GM at 725 nm) and three-photon absorption cross sections (ca. 1.6 × 10⁻⁷⁶ cm⁶s² at 1100 nm) are found for the 8PV-containing example, highlighting the potential of an “organometalation” approach to NLO-efficient organic materialsWe thank the Australian Research Council (ARC), the National Natural Science Foundation of China (51432006), the Chinese Government Ministry of Education, the Chinese Government State Administration of Foreign Experts Affairs (111 Project: B13025), and the National Science Centre of Poland (grant 2013/10/A/ST4/00114) for financial support. M. P. C. thanks the ARC for an Australian Research Fellowship and C. Q. thanks CONICYT (Chile) for a Chile PhD Scholarship Abroad

Health, Wealth, and Air Pollution: Advancing Theory and Methods

The effects of both ambient air pollution and socioeconomic position (SEP) on health are well documented. A limited number of recent studies suggest that SEP may itself play a role in the epidemiology of disease and death associated with exposure to air pollution. Together with evidence that poor and working-class communities are often more exposed to air pollution, these studies have stimulated discussion among scientists, policy makers, and the public about the differential distribution of the health impacts from air pollution. Science and public policy would benefit from additional research that integrates the theory and practice from both air pollution and social epidemiologies to gain a better understanding of this issue. In this article we aim to promote such research by introducing readers to methodologic and conceptual approaches in the fields of air pollution and social epidemiology; by proposing theories and hypotheses about how air pollution and socioeconomic factors may interact to influence health, drawing on studies conducted worldwide; by discussing methodologic issues in the design and analysis of studies to determine whether health effects of exposure to ambient air pollution are modified by SEP; and by proposing specific steps that will advance knowledge in this field, fill information gaps, and apply research results to improve public health in collaboration with affected communities