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 (TTF1TTF3) and iodine (I-2) is reported herein. TTF1TTF3 show the CT with I-2 in the CH2Cl2 solution, but they are not completely converted into cation radical state. In CT complexes of TTF1TTF3 with I-2, the charged states of Ar-S-TTFs are distinct from those in solution. TTF1 is at cation radical state, and TTF2TTF3 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)(-).