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

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 (I 2 ) is reported herein. TTF1 — TTF3 show the CT with I 2 in the CH 2 Cl 2 solution, but they are not completely converted into cation radical state. In CT complexes of TTF1 — TTF3 with I 2 , 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 (I 5 ) – , and 2‐D and 3‐D iodine networks composed of I 2 and (I 3 ) – .