Novel Tetrazine Organometallic Complexes for Nonlinear Optical Switching: a Combined Density Functional Theory and Experimental Study

Over the past decade, mono- and bi- and oligonuclear organometallic complexes have been deal of great interest by material chemists and engineers due to their remarkable nonlinear optical (NLO), magnetic and electric properties. [1] They were furthermore envisaged as powerful candidates for quantum computing, molecular devices and more interestingly as molecular switches. The definition of molecular switch implies that a compound should have two interconvertable stable forms that have a significant difference in the magnitude of, at least, one of their physico-chemical properties. [2] In the case of organometallic complexes the most expedite way to achieve such interconversion is by redox means, where one takes advantage of the different oxidations states allowed by a single or multiple metal centers that interact with each other, and with the ligands therein. It is known that the choice of an appropriate π-bridging system between the metal centers is crucial to obtain the adequate electronic environment for efficient metal-to-metal and metal-to-ligand interactions, and hence fine tune the optical, electric and magnetic macroscopic properties. Mixed-valance metal complexes from group VIII, particular Fe(II)/Fe(III) and Ru(II)/Ru(III) systems [3,4], have been successfully synthesized as stable species that possess strong metal-to-ligand charge transfer (MLCT) and inter-valence charge transfer (IVCT) absorption bands in visible and NIR regions, respectively.[5, 6] This is the case of the well known Creutz-Taube ion [(H3N)5Ru(m-pz)Ru(NH3)5]5+ (pz=pyrazine) and related compounds. Substituted 1,2,4,5-tetrazine (tz) strongly enhance both the stability and the MLCT and IVCT phenomenon’s since they act as a strong π-acceptor and can stimulate the metal-to-metal interaction. [6] In this work, we present our ongoing studies in the use of substituted 1,2,4,5-tetrazine (tz) ligands as the π-bridge between two transition metal centers, both experimentally and by means of Density Functional Theory (DFT). Synthesis and characterization by NMR, voltammetric and UV-Vis. spectra are presented. The DFT calculations were used to evaluate the nature of the electronic transitions as well as the switching of the NLO properties. The compounds showed to be great candidates for NLO switching since the magnitude of such property can change upon redox stimulus at the metal centers

A Blueprint for the Hard Problem of Consciousness

A Blueprint for the Hard Problem of Consciousness addresses the fundamental mechanism that allows physical events to transcend into subjective experiences, termed the Hard Problem of Consciousness. Consciousness is made available as the abstract product of self-referent realization of information by strange loops through the levels of processing of the brain. Readers are introduced to the concept of the Hard Problem of Consciousness and related concepts followed by a critical discourse of different theories of consciousness. Next, the author identifies the fundamental flaw of the Integrated Information Theory (IIT) and proposes an alternative that avoids the cryptic intelligent design and panpsychism of the IIT. This author also demonstrates how something can be created out of nothing without resorting to quantum theory, while pointing out neurobiological alternatives to the bottom-up approach of quantum theories of consciousness. The book then delves into the philosophy of qualia in different physiological knowledge networks (spatial, temporal and olfactory, cortical signals, for example) to explain an action-based model consistent with the generational principles of Predictive Coding, which maps prediction and predictive-error signals for perceptual representations supporting integrated goal-directed behaviors. Conscious experiences are considered the outcome of abstractions realized out of map overlays and provided by sustained oscillatory activity. The key feature of this blueprint is that it offers a perspective of the Hard Problem of Consciousness from the point of view of the subject; the experience of ‘being the subject’ is predicted to be the realization of inference inversely mapped out of hidden causes of global integrated actions. The author explains the consistencies of his blueprint with ideas of the Global Neuronal Workspace and the Adaptive Resonance Theory of consciousness as well as with the empirical evidence supporting the Integrated Information Theory. A Blueprint for the Hard Problem of Consciousness offers a unique perspective to readers interested in the scientific philosophy and cognitive neuroscience theory in relation to models of the theory of consciousness

The Impulsive Phase in Solar Flares: Recent Multi-wavelength Results and their Implications for Microwave Modeling and Observations

This short paper reviews several recent key observations of the processes occurring in the lower atmosphere (chromosphere and photosphere) during flares. These are: evidence for compact and fragmentary structure in the flare chromosphere, the conditions in optical flare footpoints, step-like variations in the magnetic field during the flare impulsive phase, and hot, dense 'chromospheric' footpoints. The implications of these observations for microwaves are also discussed.Comment: 6 pages, 5 figures, presented at 'Solar Physics with Radio Observations' Symposium, November 2012, Nagoya, Japa