The pyridazine–tetrathiafulvalene conjugates: synthesis, photophysical, and electrochemical properties

• Published in: Tetrahedron Vol. 68; no. 6; pp. 1782 - 1789
• Main Authors: Zheng, Ningjuan, Li, Bao, Ma, Changwei, Chen, Tie, Kan, Yuhe, Yin, Bingzhu
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 11-02-2012; Elsevier
• Subjects: Absorption spectra; Charge transfer; Chemistry; Conjugates; Donor–acceptor conjugate; Electrochemical behavior; Electrochemistry; Electronics; Exact sciences and technology; General and physical chemistry; Ground state; Heterocyclic compounds; Heterocyclic compounds with n hetero atom and also o and/or s, se, te hetero atoms; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Hydrates; Hydrazines; Organic chemistry; Photophysical property; Preparations and properties; Pyridazine; Tetrathiafulvalene; Voltammetry; Donor–acceptor conjugate; Tetrathiafulvalene; Charge transfer; Photophysical property; Electrochemical behavior; Pyridazine; Molecular orbital; Nitrogen heterocycle; Ground state; Molecular interaction; Energy level; Intramolecular charge transfer; Characterization; Cyclic voltammetry; Donor―acceptor conjugate; Optical properties; Pyridazine derivatives; Hydrazine; Chemical synthesis; Hydrates; Electronic properties; Condensation reaction; Optoelectronic properties; Tetrathiafulvalene derivatives; X ray diffraction; Annelation; Absorption spectrometry; Sulfur heterocycle; Electrochemical properties; Electrochemistry; Density functional method; Ultraviolet visible spectrometry
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2011.12.034

To study the electronic interactions in donor–acceptor (D–A) conjugates as a precursor of optoelectronic materials, a series monopyridazine-annulated tetrathiafulvalenes and a bispyridazine-annulated tetrathiafluvalene were synthesized by a condensation reaction of 2,3-dimethoxycarbonyl-6,7-dibutylthiotetrathiafulvalene or/and 2,3,6,7-tetramethoxycarbonyltetrathiafulvalene with hydrazine hydrate and structurally characterized by conventional chemical and physical methods. Their electronic properties have been studied experimentally by the combination of electrochemistry and UV–vis spectroscopy. All of monopyridazine-tetrathiafulvalene conjugates
7–
13 show intramolecular charge transfer interaction in ground states, which is rationalized on the basis of density functional theory. Their HOMO energy levels and
E
g
opt values were estimated to be −4.88 to −5.07 eV from cyclic voltammetry and 2.43–2.79 eV from the absorption spectra, respectively. The X-ray crystallographic analyses of the pyridazine–tetrathiafulvalene conjugates
7,
11–
13 are also reported.
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