Computational and experimental results, including absorption and emission energy maxima, electrochemical reduction potentials, LLTS, singlet excited states, and LUMO and HOMO energies, exhibit linear correlations with the Hammett constants for para-substituents σ p. Time-dependent DFT calculations are performed to compute the singlet excited state energies of these complexes so as to help interpret their UV-Vis absorption spectra. The LLTS are assigned based on the electron spin density distributions and correlated with the singlet excited states to understand the mechanism of electronic excitation and relaxation. The DFT also reveals the geometry of the lowest-lying triplet state (LLTS) of each complex that is important for emission behavior. These complexes are distorted from planarity based on both single crystal structure determinations and density functional theory (DFT) calculations of isolated molecules in acetonitrile.
#LUMO ENERGY SERIES#
Charge frustration in ligand design and functional group transfer.A series of platinum( II) biphenyl 2,2′-bipyridine complexes containing electron-donating and electron-withdrawing moieties on the 4 and 4′ positions of the bipyridine ligand exhibit emission from excited states in the 600 nm region of the spectrum upon excitation in the metal-to-ligand charge transfer transition located near 450 nm. Synthesis, characterization, DFT, and TD-DFT studies of (E)-5-((4,6-dichloro-1,3,5-triazin-2-yl)amino)-4-hydroxy-3-(phenyldiazenyl)naphthalene-2,7-diylbis(hydrogen sulfite). The Journal of Chemical Physics 2021, 155 Substituent effects in aqueous solutions of carboxylate salts studied by x-ray absorption spectroscopy at the oxygen K-edge. Color-tunable arylaminoanthraquinone dyes through hydrogen-bond-assisted charge transfer interaction. Takashi Takeda, Yotaro Kasahara, Tomoyuki Akutagawa.Synthesis, characterization, and theoretical studies of the photovoltaic properties of novel reactive azonitrobenzaldehyde derivatives. Anthracene-Based Zwitterion with a Small HOMO–LUMO Energy Gap. Ayane Kayama, Akihiro Shimizu, Ryo Shintani.Computational and Theoretical Chemistry 2022, 139, 113801. Poly(3-aminophenylboronic acid) as a Sensitive Electrical and Optical Sensor Material for Detection of Some Air Pollutants: A Computational Study. Sara Taremi, Morteza Rouhani, Zohreh Mirjafary.Fully zwitterionic diaminobenzoquinonediimines promoted by cyanoaromatic N-substituents. Bousquet, Adrien Morice, Ugo Triballier, Gabriel Canard, Pavel Lhoták, Denis Jacquemin, Simon Pascal, Olivier Siri. The Journal of Organic Chemistry 2022, 87 Solvation Effects in Organic Chemistry: A Short Historical Overview. Synthesis of Asymmetric Coupled Polymethines Based on a 7-Chloropyridobenzimidazole-8,9-dione Core.
Anastasija Gaile, Sergey Belyakov, Baiba Turovska, Nelli Batenko.
Feasibility of p-Doped Molecular Crystals as Transparent Conductive Electrodes via Virtual Screening. Tahereh Nematiaram, Alessandro Troisi.This article is cited by 11 publications. This molecular design will generate small π-conjugated donor–acceptor molecules with small Δ E H–L values. The NIR absorption responds to solvent polarity, temperature, and acid addition. 1 eV and show amphoteric redox properties and near-infrared (NIR) electronic absorption exceeding λ = 1000 nm. The zwitterions with small Δ E D–A and large φ DA have a small Δ E H–L of ca. The energy difference between the HOMO of the anion and the LUMO of the cation (Δ E D–A) and the interplanar angle between them (φ DA) have a crucial effect on Δ E H–L, and hence, on the electronic structures and optoelectronic properties of these zwitterions. To develop relatively small donor–acceptor molecules with small Δ E H–L values, we have designed and synthesized π-conjugated zwitterions composed of electron-donating anions, such as phenoxide and anthroxide, and electron-accepting cations, such as pyridinium and acridinium. Although the expansion of π-conjugation is one of the well-known approaches for designing molecules with small Δ E H–L values, such an approach inevitably gives large π-conjugated molecules sometimes suffering from synthetic difficulty and low solubility toward organic solvents. Π-Conjugated molecules with small highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gaps (Δ E H–L) have been extensively studied because of their unique optoelectronic properties.