Building up 1‐D, 2‐D, and 3‐D Polyiodide Frameworks by Finely Tuning the Size of Aryls on Ar‐S‐TTF in the Charge‐Transfer (CT) Complexes of Ar‐S‐TTFs and Iodine

Abstract

The arylthio‐substituted tetrathiafulvalenes (Ar‐S‐TTFs) are electron donors having three reversible states, neutral, cation radical, and dication. The charge‐transfer (CT) between Ar‐S‐TTFs (TTF1—TTF3) and iodine (I2) is reported herein. TTF1—TTF3 show the CT with I2 in the CH2Cl2 solution, but they are not completely converted into cation radical state. In CT complexes of TTF1—TTF3 with I2, the charged states of Ar‐S‐TTFs are distinct from those in solution. TTF1 is at cation radical state, and TTF2—TTF3 are oxidized to dication. The iodine components in complexes show various structures including 1‐D chain of V‐shaped (I5)–, and 2‐D and 3‐D iodine networks composed of I2 and (I3)–.

Noncovalent Bonds, Spectral and Thermal Properties of Substituted Thiazolo[2,3-b][1,3]thiazinium Triiodides

“…Polyiodides represent an absolute majority among polyhalide structures [16][17][18][19][20][21]. The interest in polyiodide derivatives is based on their enormous structural diversity of packing motives resulting in the formation of anionic ribbons, layers, channels and sheets [22][23][24]. The intense development of semiconductor [25][26][27][28] and nonlinear optical materials [29] based on polyiodides [30] necessitates obtaining and comprehensively investigating new molecular and crystal structures with specific properties.…”

Research Progress on Photocatalytic Reduction of CO2 Based on CsPbBr3 Perovskite Materials

“…At present, inorganic metal halides (such as CsPbX 3 ) have begun to explore in this field. Li et al [43] prepared CsPbBr 3 /TiO 2 composite by ligandassisted reprecipitation method. The composite oxidized toluene to benzaldehyde under light.…”

Synthesis and structures of polyiodide radical cation salts of donors combining tetrathiafulvalene with multiple thiophene or oligo-thiophene substituents

“…18 The tetraphenyl analogue 21 also forms a pentaiodide salt, containing the same structural motif for the radical cation pair but the pentaiodide anions are organised "end-to-end" to form a chain. 19 Complexes of unsymmetrical donors 17A, 19A and 19C Donors 17A, 19A and 19C are closely related and have just two side chains: 17A and 19A with two thiophenes and 19C with two bithiophenes. The latter two donors have an ethylene bridge at one end, but donor 17A differs from donor 19A by having a C(H)C(H)-bridge rather than and a -CH 2 CH 2bridge.…”

“…Each of the radical cations is part of a centrosymmetric faceto-face pair. In one of these the centre of symmetry lies directly between the central double bonds of the two EDT-TTF systems, and there are close S⋯S contacts of 3.3038(15) 23.870(17) 3.8690 (19) 3.888 (3) and 3.4397(16) Å between the TTF units. In the second one the donor is slipped along its long axis by ca.…”

“…18 Related donors 24 and 25 with four 3-methylphenyl or 4-methoxyphenyl groups (Scheme 3) also form salts of their dications accompanied by networks composed of triiodide anions and iodine molecules. 19 This illustrates how difficult it is to predict which polyiodide complex will form, especially bearing in mind, as Shao points out, that the dication 23 has formed from the least readily oxidized donor among compounds 21-25 according to cyclic voltammetry measurements. Crystal packing forces control the product formed, but there are numerous combinations to consider.…”