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Exploiting a template effect of 1,4-diazacycloheptane (also known as homopiperazine, Hpipe), four new hybrid iodides, (HpipeH 2 ) 2 Bi 2 I 10 ·2H 2 O, (HpipeH 2 )I(I 3 ), (HpipeH 2 ) 3 I 6 ·H 2 O, and (HpipeH 2 ) 3 (H 3 O)I 7 , were prepared and their crystal structures were solved using single crystal X-ray diffraction data. All four solid-state crystal structures feature the HpipeH 2  2+ cation alternating with Bi 2 I 10  4- , I 3  - , or I - anions and solvent water or H 3 O + cation. HpipeH 2  2+ assembles anionic and neutral building blocks into polymer structures by forming four strong (N)H···I and (N)H···O hydrogen bonds per cation, with the H···I distances ranging from 2.44 to 2.93 Å and H···O distances of 1.88-1.89 Å. These hydrogen bonds strongly affect the properties of compounds; in particular, in the case of (HpipeH 2 ) 2 Bi 2 I 10 ·2H 2 O, they ensure narrowing of the band gap down to 1.8 eV and provide high thermal stability up to 240 °C, remarkable for a hydrated molecular solid.

molecules/molecules online/molecules annual

Assembling Polyiodides and Iodobismuthates Using a Template Effect of a Cyclic Diammonium Cation and Formation of a Low-Gap Hybrid Iodobismuthate with High Thermal Stability