Search Results (10)

For designing single-molecule devices that have both conjugation systems and structural flexibility, a hyperconjugated molecule with a σ–π bond interaction is considered an ideal candidate. In the investigation of conductance at the single-molecule level, since few hyperconjugation systems have been involved, the strategy of building hyperconjugation systems and the mechanism of electron transport within this system remain unexplored. Based on the skipped-conjugated structure, we present a rational approach to construct a hyperconjugation molecule using a hydroxyl group, which serves as a bridge to interact with the conjugated fragments. The measurement of single-molecule conductance reveals a two-fold conductance enhancement of the hyperconjugation system having the ‘bridging’ hydroxyl group compared to hydroxyl-free derivatives. Theoretical studies demonstrate that the hydroxyl group in the hyperconjugation system connects the LUMO of the two conjugated fragments and opens a through-space channel for electron transport to enhance the conductance. Full article

New anti-octadecaborane(22) laser dyes have been recently introduced. However, their application in solid thin films is limited, despite being very desirable for electronics. Spectroscopic methods, photoluminescence (PL), and infrared reflection–absorption spectroscopy (IRRAS), are here used to reveal structural responses to a temperature change in thin polymer films made of π- and σ-conjugated and non-conjugated polymers and anti-octadecaborane(22) and its tetra-alkylatedderivatives. It has been observed that borane clusters are not firmly fixed within polymer matrices and that their ability for diffusion out of the polymer film is unprecedented, especially at higher temperatures. This ability is related to thermodynamic transitions of polymer macromolecular chains. PL and IRRAS spectra have revealed a clear correlation with β-transition and α-transition of polymers. The influence of structure and molecular weight of a polymer and the concentration and the substitution type of clusters on mobility of borane clusters within the polymer matrix is demonstrated. A solution is proposed that led to an improvement of the temperature stability of films by 45 °C. The well-known spectroscopic methods have proved to be powerful tools for a non-routine description of the temperature behavior of both borane clusters and polymer matrices. Full article

In 1996, we reported that silyl groups of 9,10-disilylanthracenes significantly affect the UV/Vis and fluorescence spectra. Although the results indicate that the silyl groups have strong electronic effects on anthracene, the details of the mechanisms responsible for this have not yet been clarified. This article describes the analysis of the UV/Vis and fluorescence spectra of 9,10-bis(diisopropylsilyl)anthracene by theoretical calculations. This study reveals that π conjugation of anthracene is extended by cooperation of σ–π and σ*–π* conjugation between the silyl groups and anthracene. This effect increases the transition moment of the π–π* transition of anthracene. As a result, the molecular extinction coefficient of the ¹L_a band and the fluorescence quantum yield are increased. Full article

Two 15-membered octaazamacrocyclic nickel(II) complexes are investigated by theoretical methods to shed light on their affinity forwards binding and reducing CO₂. In the first complex ¹[Ni^IIL]⁰, the octaazamacrocyclic ligand is grossly unsaturated (π-conjugated), while in the second ¹[Ni^IILH]²⁺ one, the macrocycle is saturated with hydrogens. One and two-electron reductions are described using Mulliken population analysis, quantum theory of atoms in molecules, localized orbitals, and domain averaged fermi holes, including the characterization of the Ni-C_CO2 bond and the oxidation state of the central Ni atom. It was found that in the [NiLH] complex, the central atom is reduced to Ni⁰ and/or Ni^I and is thus able to bind CO₂ via a single σ bond. In addition, the two-electron reduced ³[NiL]²⁻ species also shows an affinity forwards CO₂. Full article

In this work, we report solvent-induced complexation properties of a new N₂S₂ tetradentate bis-thiosemicarbazone ligand (H₂L^I), prepared by the condensation of 4-phenylthiosemicarbazide with bis-aldehyde, namely 2,2’-(ethane-1,2-diylbis(oxy)dibenzaldehyde, towards nickel(II). Using ethanol as a reaction medium allowed the isolation of a discrete mononuclear homoleptic complex [NiL^I] (1), for which its crystal structure contains three independent molecules, namely 1-I, 1-II, and 1-III, in the asymmetric unit. The doubly deprotonated ligand L^I in the structure of 1 is coordinated in a cis-manner through the azomethine nitrogen atoms and the thiocarbonyl sulfur atoms. The coordination geometry around metal centers in all the three crystallographically independent molecules of 1 is best described as the seesaw structure. Interestingly, using methanol as a reaction medium in the same synthesis allowed for the isolation of a discrete mononuclear homoleptic complex [Ni(L^II)₂] (2), where L^II is a monodeprotonated ligand 2-(2-(2-(2-(dimethoxymethyl)phenoxy)ethoxy)benzylidene)-N-phenylhydrazine-1-carbothioamide (HL^II). The ligand L^II was formed in situ from the reaction of L^I with methanol upon coordination to the metal center under synthetic conditions. In the structure of 2, two ligands L^II are coordinated in a trans-manner through the azomethine nitrogen atom and the thiocarbonyl sulfur atom, also yielding a seesaw coordination geometry around the metal center. The charge and energy decomposition scheme ETS-NOCV allows for the conclusion that both structures are stabilized by a bunch of London dispersion-driven intermolecular interactions, including predominantly N–H∙∙∙S and N–H∙∙∙O hydrogen bonds in 1 and 2, respectively; they are further augmented by less typical C–H∙∙∙X (where X = S, N, O, π), CH∙∙∙HC, π∙∙∙π stacking and the most striking, attractive long-range intermolecular C–H∙∙∙Ni preagostic interactions. The latter are found to be determined by both stabilizing Coulomb forces and an exchange-correlation contribution as revealed by the IQA energy decomposition scheme. Interestingly, the analogous long-range C–H∙∙∙S interactions are characterized by a repulsive Coulomb contribution and the prevailing attractive exchange-correlation constituent. The electron density of the delocalized bonds (EDDB) method shows that the nickel(II) atom shares only ~0.8|e| due to the σ-conjugation with the adjacent in-plane atoms, demonstrating a very weak σ-metalloaromatic character. Full article

Metastable colloids made of crystalline and/or non-crystalline matters render abilities of photonic resonators susceptible to chiral chemical and circularly polarized light sources. By assuming that μm-size colloids and co-colloids consisting of π- and/or σ-conjugated polymers dispersed into an optofluidic medium are artificial models of open-flow, non-equilibrium coacervates, we showcase experimentally resonance effects in chirogenesis and photochirogenesis, revealed by gigantic boosted chiroptical signals as circular dichroism (CD), optical rotation dispersion, circularly polarized luminescence (CPL), and CPL excitation (CPLE) spectral datasets. The resonance in chirogenesis occurs at very specific refractive indices (RIs) of the surrounding medium. The chirogenesis is susceptible to the nature of the optically active optofluidic medium. Moreover, upon an excitation-wavelength-dependent circularly polarized (CP) light source, a fully controlled absolute photochirogenesis, which includes all chiroptical generation, inversion, erase, switching, and short-/long-lived memories, is possible when the colloidal non-photochromic and photochromic polymers are dispersed in an achiral optofluidic medium with a tuned RI. The hand of the CP light source is not a determining factor for the product chirality. These results are associated with my experience concerning amphiphilic polymerizable colloids, in which, four decades ago, allowed proposing a perspective that colloids are connectable to light, polymers, helix, coacervates, and panspermia hypotheses, nuclear physics, biology, radioisotopes, homochirality question, first life, and cosmology. Full article

A computational study is presented in which two strategies of ligand modifications have been explored to invert the relative energy of the metal-to-ligand charge transfer (MLCT) and metal-centered (MC) state in Fe(II)-polypyridyl complexes. Replacing the bipyridines by stronger $\sigma$ donors increases the ligand-field strength and pushes the MC state to higher energy, while the use of ligands with a larger $\pi$ conjugation leads to lower MLCT energies. Full article

We synthesized four C₆₀-(light-harvesting antenna) dyads C₆₀ (>CPAF-C_n) (n = 4, 9, 12, or 18) 1-C_n for the investigation of their broadband nonlinear absorption effect. Since we have previously demonstrated their high function as two-photon absorption (2PA) materials at 1000 nm, a different 2PA wavelength of 780 nm was applied in the study. The combined data taken at two different wavelength ranges substantiated the broadband characteristics of 1-C_n. We proposed that the observed broadband absorptions may be attributed by a partial π-conjugation between the C₆₀ > cage and CPAF-C_n moieties, via endinitrile tautomeric resonance, giving a resonance state with enhanced molecular conjugation. This transient state could increase its 2PA and excited-state absorption at 800 nm. In addition, a trend of concentration-dependent 2PA cross-section (σ₂ ) and excited-state absorption magnitude was detected showing a higher σ value at a lower concentration that was correlated to increasing molecular separation with less aggregation for dyads C₆₀(>CPAF-C₁₈) and C₆₀(>CPAF-C₉), as better 2PA and excited-state absorbers. Full article

Combined computational and experimental strategies for the systematic design of chemical sensor arrays using carbonitrile neutral receptors are presented. Binding energies of acetonitrile, n-pentylcarbonitrile and malononitrile with Ca(II), Mg(II), Be(II) and H⁺ have been investigated with the B3LYP, G3, CBS-QB3, G4 and MQZVP methods, showing a general trend H⁺ > Be(II) > Mg(II) > Ca(II). Hydrogen bonding, donor-acceptor and cation-lone pair electron simple models were employed in evaluating the performance of computational methods. Mg(II) is bound to acetonitrile in water by 12.5 kcal/mol, and in the gas phase the receptor is more strongly bound by 33.3 kcal/mol to Mg(II) compared to Ca(II). Interaction of bound cations with carbonitrile reduces the energies of the MOs involved in the proposed σ-p conjugated network. The planar malononitrile-Be(II) complex possibly involves a π-network with a cationic methylene carbon. Fabricated potentiometric chemical sensors show distinct signal patterns that can be exploited in sensor array applications. Full article

The HOMA (Harmonic Oscillator Model of Aromaticity) index, reformulated in 1993, has been very often applied to describe π-electron delocalization for mono- and polycyclic π-electron systems. However, different measures of π-electron delocalization were employed for the CC, CX, and XY bonds, and this index seems to be inappropriate for compounds containing heteroatoms. In order to describe properly various resonance effects (σ-π hyperconjugation, n-π conjugation, π-π conjugation, and aromaticity) possible for heteroatomic π-electron systems, some modifications, based on the original HOMA idea, were proposed and tested for simple DFT structures containing C, N, and O atoms. An abbreviation HOMED was used for the modified index. Full article