Game of Frontier Orbitals: A View on the Rational Design of Novel Charge-Transfer Materials

Since the first application of frontier molecular orbitals (FMOs) to rationalize stereospecificity of pericyclic reactions, FMOs have remained at the forefront of chemical theory. Yet, the practical application of FMOs in the rational design and synthesis of novel charge transfer materials remains under-appreciated. In this Perspective, we demonstrate that molecular orbital theory is a powerful and universal tool capable of rationalizing the observed redox/optoelectronic properties of various aromatic hydrocarbons in the context of their application as charge-transfer materials. Importantly, the inspection of FMOs can provide instantaneous insight into the interchromophoric electronic coupling and polaron delocalization in polychromophoric assemblies, and therefore is invaluable for the rational design and synthesis of novel materials with tailored properties

Evolution, present status and issues concerning small tank systems in Sri Lanka [Small tanks in Sri Lanka: evolution, present status and issues]

Tank irrigationSmall scale systemsHistoryIrrigation systemsDesignMaintenanceHydrologyPollutionIrrigation managementCultivationFarming systemsWells

Novel Synthesis and Structures of Tris-Annelated Benzene Donors for the Electron-Density Elucidation of the Classical Mills−Nixon Effect

A versatile method for the high-yield synthesis of various tris-, bis-, and mono-annelated benzenes (as well as cyclooctatetraene) is based on the Pd-catalyzed coupling of three (or four) ethylenic units comprised of α,β-dibromoalkenes and α‘-alkenyl Grignard reagentsall carried out in a single pot. The particular application to tris(bicyclopentyl)-annelated benzene yields the syn isomer 1s in high purity; X-ray diffraction analysis confirms the aromatic bond alternation relevant to the Mills−Nixon effect. Most importantly, the efficient synthesis of 1s crystals of extraordinary quality allows us (for the first time) to make precise electron-density measurements of the “banana-type” distortion and the ellipticity (π-character) of the various aromatic C−C bondssufficient to identify the electronic origin of the classical Mills−Nixon effect. The unique electron-donor properties of tris-annelated benzenes also relate to their highly reversible one-electron oxidation potentials even in nonpolar solvents

Preparation and Structures of Crystalline Aromatic Cation-Radical Salts. Triethyloxonium Hexachloroantimonate as a Novel (One-Electron) Oxidant

Triethyloxonium hexachloroantimonate [Et3O+SbCl6-] is a selective oxidant of aromatic donors (ArH), and it allows the facile preparation and isolation of crystalline paramagnetic salts [ArH+•, SbCl6-] for the X-ray structure determination of various aromatic cation radicals. The mechanistic relationship between the Meerwein salt [Et3O+SbCl6-] and the pure Lewis acid oxidant SbCl5 is based on a prior ethyl transfer from oxygen to chlorine within the ion pair

Disproportionation and Structural Changes of Tetraarylethylene Donors upon Successive Oxidation to Cation Radicals and to Dications

The stepwise (one-electron) chemical oxidation of the tetraphenylethylene donor and its substituted analogues (D) can be carried out by electron exchange with aromatic cations or antimony(V) oxidants to selectively afford the cation radical (D+•) initially and then the dication (D2+). The ready interchange of the latter establishes the facile disproportionation (i.e., 2D+• ⇌ D2+ + D) that was originally examined by only transient electrochemical techniques. The successful isolations of the crystalline salts of the tetraanisylethylene cation radical (1+•) as well as the tetraanisylethylene dication (12+) allow X-ray diffraction analysis (for the first time) to quantify the serial changes in the molecular structure upon successive oxidations. Five structural parameters (d, l, θ, φ, and q) are identified as quantitative measures of changes in bond (CαCβ, Cαanisyl) lengths, dihedral (CαCβ)/torsional (anisyl) angles, and quinoidal (anisyl) distortion attendant upon the removal of first one-electron and then another electron from the tetraanisylethylene framework. The linear variation of all five parameters in Chart 3 point to a strongly coupled relaxation of tetraanisylethylene (involving simultaneous changes of d, l, θ, φ, and q) to a severely twisted dication. Most noteworthy is the structure of the cation radical 1+• with d, l, θ, φ, and q values that are exactly one-half those of the dication. The complex molecular changes accompanying the transformation:  D → D+• → D2+ bear directly on the donor properties and the disproportionation processes of various tetraarylethylenes

Scale-Free Phenomena in Communication Networks: A Cross-Atlantic Comparison

?Small-world networks? have a high degree of local clustering or cliqueness, like a regular lattice and a relatively short average minimum path, like a completely random network. The huge appeal of ?small-world networks? lies in the impact they are said to have on dynamical systems. In a transportation network, ?small-world? topology could improve the flow of people or goods through the network, which has important implications for the design of such networks. Preliminary research has shown that ?small-world network? phenomenon can arise in traffic networks possessing ?small-world? network topology (i.e., in a network that has a structure somewhere in between a regular lattice and random graph) and that, at least under certain circumstances, traffic appears to flow more efficiently through a network with such topology (Schintler and Kulkarni, 2000). This paper will explore this further through simulation under varying assumptions regarding the size of the network (i.e., in terms of number of nodes and edges), the level of traffic in the network, the uniformity of nodes and edges and the information levels of travelers in the network. The simulations will be done using the random rewiring process introduced by Watts and Strogatz (1998), where each time the network is rewired, the distribution of traffic and congestion through the network, and the ?small-world? network parameters, shortest average minimum path and clustering coefficient, will be examined. Traffic flow will be estimated using a gravity model framework and a route choice optimization program. The simulations will also be used to reveal whether or not there are certain nodes or links that suffer at the expense of the entire network becoming more efficient. In addition, the possibility of a self-organised criticality (SOC) structure will be examined. The concept, introduced by Bak et al.,(1987), gained a great deal of attention in past decades for its capability to explore the significant and structural transformation of a dynamic system. SOC sets out how prominent exogenous forces together with strong localized interactions at the micro level lead a system to a critical state at the macro-level. A further step in our analysis is the investigation of whether a power-law distribution, characteristic of the SOC state, evolves in the traffic network. While ?small-world? network topology may be shown to improve the efficiency of traffic flow through a network, it should be recognized that ?small-world? networks are sparse by nature. The shut down or major disruption of any link in such a network, particularly one with heavy congestion, could provoke significant disorder. This paper will also explore the effect that disruptions of this nature have on networks designed with a high degree of local clustering and a short average minimum path. The fact that a ?small-world? network is sparse also raises other issues for the transportation planner. If ?small-world? topology is in fact a desirable property for transportation networks, how do we transform existing networks to produce these results? Unlike other networks, such as those for telecommunications or socialization, a transportation network cannot be rewired to achieve a more efficient network structure. This issue will also be addressed in the paper. REFERENCES Bak, P., C. Tang, and K. Wiesenfeld (1987), ?Self-Organised Criticality?, Physical Review Letters, Vol. 59 (4), pp. 381-384. Watts, D.J. and S.H. Strogatz (1998). ?Collective Dynamics of ?Small-World? Networks? Nature, Vol 393, 4, pp. 440-442. Schintler, L.A. and R. Kulkarni (2000). ?The Emergence of Small-World Phenonmenon in Urban Transportation Networks? in Reggiani, A. (ed.), Spatial Economic Science: New Frontiers in Theory and Methodology, Springer-Verlag, Berlin-NewYork, pp. 419-434.

Vertical vs. Adiabatic Ionization Energies in Solution and Gas-Phase: Probing Ionization-Induced Reorganization in Conformationally-Mobile Bichromophoric Actuators Using Photoelectron Spectroscopy, Electrochemistry and Theory

Ionization-induced structural and conformational reorganization in various π-stacked dimers and covalently linked bichromophores is relevant to many processes in biological systems and functional materials. In this work, we examine the role of structural, conformational, and solvent reorganization in a set of conformationally mobile bichromophoric donors, using a combination of gas-phase photoelectron spectroscopy, solution-phase electrochemistry, and density functional theory (DFT) calculations. Photoelectron spectral analysis yields both adiabatic and vertical ionization energies (AIE/VIE), which are compared with measured (adiabatic) solution-phase oxidation potentials (Eox). Importantly, we find a strong correlation of Eox with AIE, but not VIE, reflecting variations in the attendant structural/conformational reorganization upon ionization. A careful comparison of the experimental data with the DFT calculations allowed us to probe the extent of charge stabilization in the gas phase and solution and to parse the reorganizational energy into its various components. This study highlights the importance of a synergistic approach of experiment and theory to study ionization-induced structural and conformational reorganization