Structural and Electronic Characteristics of Thienyl(aryl)iodonium Triflates

Abstract

A general strategy toward the synthesis of aryliodonium triflate salts has been exploited to afford derivatives that incorporate thiophene and bithiophene components. Both mono- and bis(iodonium) salts have been realized, and a series of bithienyl(aryl)iodonium triflates with increasingly electron-withdrawing substituents on the aryl moiety have been synthesized. X-ray crystallographic analysis of four derivatives (4a, 4b, 6b, and 8c) demonstrates that the solid-state organization of these salts incorporates extensive networks of secondary bonding interactions between the cationic iodonium centers and the triflate counterions. UV-vis spectroscopic analysis shows that the electronic interactions between pendent aryl and heteroaryl groups across the iodonium center can be dictated by substitution. Furthermore, the energy of the HOMO-LUMO gap decreases substantially in weakly or noncoordinating solvents.

Charge carrier mobility and electronic properties of Al(Op)3: impact of excimer formation

“…3) confirm that the complex was successfully grown onto the quartz substrate. Due to the solvatochromic effect, the absorption bands have different relative intensities and result in a slight shift [28–29]. Consequently, the HOMO–LUMO gap in the thin film is 2.60 eV, which is slightly narrower than in solution.…”

Efficient and General One‐Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations

“…By decreasing the temperature, salts 3l-n could be obtained in excellent yields (entries [12][13][14]. Heteroaryl salt 3n has previously been synthesized in several steps via the corresponding stannane, [28] which further illuminates the efficiency and environmental friendliness of our procedure. Naphthalene and biphenyl were too reactive also at low temperatures, and failed to give any iodonium salts.…”

Chemistry of Polyvalent Iodine

“…Numerous X-ray structures of aryliodonium salts have been reported in the older literature. The more recent structural studies include the X-ray structure reports on (2-methoxy-5-methylphenyl)(4-methoxy-2-methylphenyl)iodonium trifluoroacetate,692 diaryl zwitterionic iodonium compound PhI + C 6 H 4 -4-SO 2 N − Tf,693 1-naphthylphenyliodonium tetrafluoroborate and 1-naphthylphenyliodonium tetrakis(pentafluorophenyl)gallate,694 and the study of structural and electronic characteristics of thienyl(aryl)iodonium triflates 695…”