Charge-transfer materials based on organic donors and acceptors have been under investigation, beginning with the first reports of conducting salts of organocyanide acceptors such as TCNQ. Charge-transfer compounds of the pi-electron acceptor 7,7,8,8,-tetracyanoquinodimethane (TCNQ) show unusual electrical and magnetic properties. The form of TCNQ has a dramatic effect on the properties of the kinds of charge-transfer compounds. In order to further study the vibrational spectroscopy of the organic semiconductor, two kinds of (1:1) charge transfer compounds of TCNQ and [RBz(4-CH3)Py][TCNQ](R==Br(1), I (2)) were synthesized and characterized by elemental analysis, infrared spectrum and Raman spectrum. The tested results of elementary analysis of the charge transfer compounds (1) and (2) were consistent with theoretical values. The IR and Raman spectra of (1) and (2) which indicate the presence of a type of TCNQ species, general speaking, the C[triple bond]N stretching frequencies around 2200 cm(-1), were used to determine the average charge on the TCNQ units, v(CN)for the neutral TCNQ molecule is higher than 2200 cm(-1)), however, v(CN) for the compounds is from 2185 to 2156 cm(-1), both shift to lower frequencies, which were consistent with the frequencies of the TCNQ radical anion In conclusion, the results of IR and Raman spectrum were consistent with the TCNQ radical anion in the compounds, namely TCNQ-.
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J Phys Condens Matter
January 2025
Department of Physics and Astronomy, Jorgensen Hall, University of Nebraska-Lincoln, Lincoln, NE 68588-0299, United States of America.
Evidence of chirality was observed at the Fe metal center in Fe(III) spin crossover coordination salts [Fe(qsal)][Ni(dmit)] and [Fe(qsal)](TCNQ)from x-ray absorption (XAS) spectroscopy at the Fe 2pcore threshold. Based on the circularly polarized XAS data, the x-ray natural circular dichroism for [Fe(qsal)][Ni(dmit)] and [Fe(qsal)](TCNQ)is far stronger than seen for [Fe(qsal)]Cl suggesting this natural circular dichroism signature is a ligand effect rather than a result of just a loss of octahedral symmetry on the Fe core. The larger the chiral effects in the Fe 2p core to bound XAS, the greater the perturbation of the Fe 2pto 2pspin-orbit splitting seen in the XAS spectra.
View Article and Find Full Text PDFMaterials (Basel)
November 2024
Institute of Chemistry, Jan Kochanowski University, Uniwersytecka St. 7G, PL-25406 Kielce, Poland.
7,7',8,8'-tetracyanoquinodimethane (TCNQ) is one of the most widely used effective surface electron acceptors in organic electronics and sensors, which opens up a very interesting field in electrochemical applications. In this review article, we outline the historical context of electrochemically stable selective electrode materials based on TCNQ and its derivatives and their development, their electrochemical characteristics, and the experimental aspects of their electrochemical applications. TCNQ-modified electrodes are characterized by long-term stability, reproducibility, and a low detection limit compared to other sensors; thus, their use can increase determination speed and flexibility and reduce investigation costs.
View Article and Find Full Text PDFJ Comput Chem
January 2025
School of Physics, The University of Sydney, Sydney, New South Wales, Australia.
Using first principles calculations we investigate cobalt-coordinated tetracyanoquinodimethane (R-CoTCNQ) as a potential catalyst for the CO electroreduction reaction (COERR). We determine that exchange-correlation functionals beyond the generalized gradient approximation (GGA) are required to accurately describe the spin properties of R-CoTCNQ, therefore, the meta-GGA rSCAN functional is used in this study. The free energy COERR reaction pathways are calculated for the reduced catalyst ([R-CoTCNQ]) with reaction products HCOOH and HCHO predicted depending on our choice of electrode potential.
View Article and Find Full Text PDFJ Phys Chem B
December 2024
Materials Department, University of California at Santa Barbara, Santa Barbara, California 93117, United States.
The distribution of counterions and dopants within electrically doped semicrystalline conjugated polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT), plays a pivotal role in charge transport. The distribution of counterions in doped films of P3HT with controlled crystallinity was examined using polarized resonant soft X-ray scattering (P-RSoXS). The changes in scattering of doped P3HT films containing trifluoromethanesulfonimide (TFSI) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (FTCNQ) as counterions to the charge carriers revealed distinct differences in their nanostructure.
View Article and Find Full Text PDFJ Chem Theory Comput
December 2024
Department of Chemistry and Biochemistry, Kent State University, Kent, Ohio 44242, United States.
A density functional theory framework is developed to study electronic excited states affected by an anisotropic dielectric environment. In particular, an anisotropic dielectric screened range-separated hybrid (SRSH[r]) functional is defined and combined with an anisotropic polarizable continuum model (PCM) implemented through a generalized Poisson equation solver. We develop the SRSH-PCM(r) approach and use it to quantify the effect of anisotropy on an excited charge transfer (CT) state energy.
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