Phthalocyanine-nanocarbon ensembles: From discrete molecular and supramolecular systems to hybrid nanomaterials

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Accounts of Chemical Research, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ar5004384Conspectus Phthalocyanines (Pcs) are macrocyclic and aromatic compounds that present unique electronic features such as high molar absorption coefficients, rich redox chemistry, and photoinduced energy/electron transfer abilities that can be modulated as a function of the electronic character of their counterparts in donor-acceptor (D-A) ensembles. In this context, carbon nanostructures such as fullerenes, carbon nanotubes (CNTs), and, more recently, graphene are among the most suitable Pc companions. Pc-C60 ensembles have been for a long time the main actors in this field, due to the commercial availability of C60 and the ell-established synthetic methods for its functionalization. As a result, many Pc-C60 architectures have been prepared, featuring different connectivities (covalent or supramolecular), intermolecular interactions (self-organized or molecularly dispersed species), and Pc HOMO/LUMO levels. All these elements provide a versatile toolbox for tuning the photophysical properties in terms of the type of process (photoinduced energy/electron transfer), the nature of the interactions beteen the electroactive units (through bond or space), and the kinetics of the formation/decay of the photogenerated species. Some recent trends in this field include the preparation of stimuli-responsive multicomponent systems ith tunable photophysical properties and highly ordered nanoarchitectures and surface-supported systems shoing high charge mobilities. A breakthrough in the Pc-nanocarbon field as the appearance of CNTs and graphene, hich opened a ne avenue for the preparation of intriguing photoresponsive hybrid ensembles shoing light-stimulated charge separation. The scarce solubility of these 1-D and 2-D nanocarbons, together ith their loer reactivity ith respect to C60 stemming from their less strained sp2 carbon netorks, has not meant an unsurmountable limitation for the preparation of variety of Pc-based hybrids. These systems, hich sho improved solubility and dispersibility features, bring together the unique electronic transport properties of CNTs and graphene ith the excellent light-harvesting and tunable redox properties of Pcs. A singular and distinctive feature of these Pc-CNT/graphene (single- or fe-layers) hybrid materials is the control of the direction of the photoinduced charge transfer as a result of the band-like electronic structure of these carbon nanoforms and the adjustable electronic levels of Pcs. Moreover, these conjugates present intensified light-harvesting capabilities resulting from the grafting of several chromophores on the same nanocarbon platform.In this Account, recent progress in the construction of covalent and supramolecular Pc-nanocarbon ensembles is summarized, ith a particular emphasis on their photoinduced behavior. e believe that the high degree of control achieved in the preparation of Pc-carbon nanostructures, together ith the increasing knoledge of the factors governing their photophysics, ill allo for the design of next-generation light-fueled electroactive systems. Possible implementation of these Pc-nanocarbons in high performance devices is envisioned, finally turning into reality much of the expectations generated by these materialsFinancial support from the Spanish MICINN (CTQ2011-24187/BQU), the Comunidad de Madrid (S2013/MIT-2841 FOTOCARBON) and the EU (“SO2S” FP7-PEOPLE-2012-ITN, no.: 316975) is acknowledge

The Next Generation Global Gravitational Wave Observatory: The Science Book

The next generation of ground-based gravitational-wave detectors will observe coalescences of black holes and neutron stars throughout the cosmos, thousands of them with exceptional fidelity. The Science Book is the result of a 3-year effort to study the science capabilities of networks of next generation detectors. Such networks would make it possible to address unsolved problems in numerous areas of physics and astronomy, from Cosmology to Beyond the Standard Model of particle physics, and how they could provide insights into workings of strongly gravitating systems, astrophysics of compact objects and the nature of dense matter. It is inevitable that observatories of such depth and finesse will make new discoveries inaccessible to other windows of observation. In addition to laying out the rich science potential of the next generation of detectors, this report provides specific science targets in five different areas in physics and astronomy and the sensitivity requirements to accomplish those science goals. This report is the second in a six part series of reports by the GWIC 3G Subcommittee: i) Expanding the Reach of Gravitational Wave Observatories to the Edge of the Universe, ii) The Next Generation Global Gravitational Wave Observatory: The Science Book (this report), iii) 3G R&D: R&D for the Next Generation of Ground-based Gravitational Wave Detectors, iv) Gravitational Wave Data Analysis: Computing Challenges in the 3G Era, v) Future Ground-based Gravitational-wave Observatories: Synergies with Other Scientific Communities, and vi) An Exploration of Possible Governance Models for the Future Global Gravitational-Wave Observatory Network

Planck 2015 results. XIV. Dark energy and modified gravity

We study the implications of Planck data for models of dark energy (DE) and modified gravity (MG), beyond the cosmological constant scenario. We start with cases where the DE only directly affects the background evolution, considering Taylor expansions of the equation of state, principal component analysis and parameterizations related to the potential of a minimally coupled DE scalar field. When estimating the density of DE at early times, we significantly improve present constraints. We then move to general parameterizations of the DE or MG perturbations that encompass both effective field theories and the phenomenology of gravitational potentials in MG models. Lastly, we test a range of specific models, such as k-essence, f(R) theories and coupled DE. In addition to the latest Planck data, for our main analyses we use baryonic acoustic oscillations, type-Ia supernovae and local measurements of the Hubble constant. We further show the impact of measurements of the cosmological perturbations, such as redshift-space distortions and weak gravitational lensing. These additional probes are important tools for testing MG models and for breaking degeneracies that are still present in the combination of Planck and background data sets. All results that include only background parameterizations are in agreement with LCDM. When testing models that also change perturbations (even when the background is fixed to LCDM), some tensions appear in a few scenarios: the maximum one found is \sim 2 sigma for Planck TT+lowP when parameterizing observables related to the gravitational potentials with a chosen time dependence; the tension increases to at most 3 sigma when external data sets are included. It however disappears when including CMB lensing

Observational signatures of modified gravity on ultra-large scales

Extremely large surveys with future experiments like Euclid and the SKA will soon allow us to access perturbation modes close to the Hubble scale, with wavenumbers $k\sim {\mathcal{H}}.$ If a modified gravity (MG) theory is responsible for cosmic acceleration, then the Hubble scale is a natural regime for deviations from General Relativity (GR) to become manifest. However, the majority of studies to date have concentrated on the consequences of alternative gravity theories for the subhorizon, quasi-static regime. In this paper, we investigate how modifications to the gravitational field equations affect perturbations around the Hubble scale. We choose functional forms to represent the generic scale-dependent behavior of gravity theories that modify GR at long wavelengths, and study the resulting deviations of ultra-large-scale relativistic observables from their GR behavior. We find that these are small unless modifications to the field equations are drastic. The angular dependence and redshift evolution of the deviations is highly parameterization- and survey-dependent, however, and so they are possibly a rich source of MG phenomenology if they can be measured