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

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

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

Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance

Reduced graphene oxide (RGO)-porphyrin (TPP) nanohybrids (RGO-TPP 1 and RGO-TPP 2) were prepared by two synthetic routes that involve functionalization of the RGO using diazonium salts. The microscopic structures, morphology, photophysical properties and nonlinear optical performance of the resultant RGO-TPP nanohybrids were investigated. The covalent bonding of the porphyrin-functionalized-RGO nanohybrid materials was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin units to the surface of the RGO by diazotization significantly improves the solubility and ease of processing of these RGO-based nanohybrid materials. Ultraviolet/visible absorption and steady-state fluorescence studies indicate considerable π-π interactions and effective photo-induced electron and/or energy transfer between the porphyrin moieties and the extended π-system of RGO. The nonlinear optical properties of RGO-TPP 1 and RGO-TPP 2 were investigated by open-aperture Z-scan measurements at 532 nm with both 4 ns and 21 ps laser pulses, the results showing that the chemical nanohybrids exhibit improved nonlinear optical properties compared to those of the benchmark material C60, and the constituent RGO or porphyrins.Financial support from the National Natural Science Foundation of China (51432006, 50925207, 51172100), the Ministry of Science and Technology of China for the International Science Linkages Program (2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (IRT14R23), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (B13025), and 100 Talents Program of CAS are gratefully acknowledged. M.G.H., C.Z. and M.P.C. thank the Australian Research Council (ARC) for support

Syntheses and Optical Properties of Azo-Functionalized Ruthenium Alkynyl Complexes

We thank the Australian Research Council (ARC), the National Natural Science Foundation of China (51432006), and the Chinese Government Ministry of Education and State Administration of Foreign Experts Affairs (111 Project: B13025) for financial support. M.P.C. thanks the ARC for an Australian Research Fellowship

Nonlinear optical properties of meso-Tetra(fluorenyl)porphyrins peripherally functionalized with one to four ruthenium alkynyl substituents

The synthesis of a series of four porphyrin derivatives based on a meso-tetrafluorenylporphyrin core functionalized with one to four trans-chlorobis(dppe)ruthenium alkynyl units (dppe = 1,2-bis(diphenylphosphino)ethane) at the periphery, together with cyclic voltammetry (CV) and UV–Vis absorption and emission spectroscopy studies, are reported. In these multipolar assemblies, the organoruthenium endgroups are potential electron-donors and the central porphyrin core is a potential electron-acceptor. The third-order nonlinear optical (NLO) responses have been assessed by Z-scan, revealing that these extended π-networks incorporating polarizable organometallic units behave as nonlinear absorbers in the near-IR range. The role of the peripheral transition metal centers on the third-order NLO properties is discussed

Synthesis, Optical, Electrochemical, and Theoretical Studies of Dipolar Ruthenium Alkynyl Complexes with Oligo(phenylenevinylene) Bridges

We thank the Australian Research Council (ARC), the National Natural Science Foundation of China (51432006), the Chinese Government Ministry of Education, and the Chinese Government State Administration of Foreign Experts Affairs (111 Project: B13025). M.P.C. thanks the ARC for an Australian Research Fellowship and C.Q. thanks CONICYT (Chile) for a Chile PhD Scholarship Abroad

Mixed-metal cluster chemistry. 39. Syntheses and X-ray structures of Mo 3 Ir 3 (μ 4 -η 2 -CO)(μ 3 -CO)(CO) 10 (η 5 -C 5 H 5 ) 3 and Mo 3 RhIr 3 (μ-CO) 4 (CO) 7 (η 5 -C 5 H 5 ) 3 (η 5 -C 5 Me 5 )

We thank the Australian Research Council (ARC) for support ofthis work. J.F. was the recipient of a China Scholarship Council ANUPostgraduate Scholarship and M.D.R. was the recipient of anAustralian Postgraduate Awar

Hybrids of gold nanoparticles and oligo(p-phenyleneethynylene)s end-functionalized with alkynylruthenium groups: Outstanding two-photon absorption in the second biological window

Oligo(p-phenyleneethynylene)s (OPEs) end-capped with (alkynyl)bis(diphosphine)ruthenium and thiol/thiolate groups stabilize ca. 2 nm diameter gold nanoparticles (AuNPs). The morphology, elemental composition and stability of the resultant organometallic OPE/AuNP hybrid materials have been defined using a combination of molecular- and nano-material chacterization techniques. The hybrids display long-term stability in solution (more than a month), good solubility in organic solvents, reversible ruthenium-centered oxidation, and transparency beyond 800 nm, and possess very strong nonlinear absorption activity at the first biological window, and unprecedented two-photon absorption activity in the second biological window (σ2 up to 38,000 GM at 1,050 nm).We thank the Australian Research Council (DP170100411: M. G. H. and M. S.) and the National Science Centre (NCN) Poland (UMO-2016/22/M/ST4/00275: J. K. Z. and M. S.) for support of this work. C. Q. thanks Becas Chile (Agencia Nacional de Investigación y Desarrollo) for financial support in the form of a PhD scholarship (2015-72160061), J. P. L. M. thanks the Australian Government for an Australian Postgraduate Award, J. D. thanks the China Scholarship Council and the Australian National University for a CSC-ANU scholarship, and J. K. Z. thanks the Foundation for Polish Science (FNP) for support. The authors acknowledge the facilities, and the scientific and technical assistance, of the Australian Microscopy & Microanalysis Research Facility and the Centre of Advanced Microscopy at the Australian National University

Letter Ruling 99-1: Electronic Retailers

The synthesis and characterization of a set of redox-active iron and ruthenium alkynyl complexes of general formula [[M]­Cl_{(1–<i>p</i>)}{CCC₆H_5–<i>m</i>(CCFlu)_<i>m</i>}_(1+<i>p</i>)]­[PF₆]_<i>n</i> are reported (<i>n</i> = 0–1; <i>m</i> = 1–2; [M] = [Fe­(η⁵-C₅Me₅)­(κ²-dppe)] and <i>p</i> = 1 or [M] = [<i>trans</i>-Ru­(κ²-dppe)₂] and <i>p</i> = 0–1). The linear and third-order nonlinear optical properties of these new organometallic complexes featuring phenylalkynyl ligands functionalized by 2-fluorenyl (Flu) groups were studied in their stable redox states. Their first electronic transitions are assigned with the help of DFT calculations. We show here that these compounds possess significant third-order NLO responses in the near-IR range for molecules of their size. In particular, the remarkably large 2PA activities of the new Ru­(II) compounds in the 600–800 nm range (<i>Z</i>-scan) make them attractive nonlinear chromophores. Structure–property studies emphasize the importance of para- versus meta-connection of the 2-fluorenylethynyl units on the phenylalkynyl core and reveal that upon progressing from mono- to bis-alkynyl complexes a further increase of the 2PA cross section can be obtained while maintaining linear transparency in the visible range