Iodine Release and Recovery, Influence of Polyiodide Anions on Electrical Conductivity and Nonlinear Optical Activity in an Interdigitated and Interpenetrated Bipillared-Bilayer Metal–Organic Framework

Abstract

{[Cu6(pybz)8(OH)2]·I5(–)·I7(–)}n (1), obtained hydrothermally by using iodine molecules as a versatile precursor template, consists of a cationic framework with two types of zigzag channels, which segregate I5(–) and I7(–) anions. The framework exhibits the first observed bipillared-bilayer structure featuring both interdigitation and interpenetration. 1 displays high framework stability in both acidic (HCl) and alkaline (NaOH) solutions. 1 slowly releases iodine in dry methanol to give [Cu6(pybz)8(OH)2](I–)2·3.5CH3OH (1′) and partially recovers iodine from cyclohexane to form [Cu6(pybz)8(OH)2](I–)2·xI2 (1″). Differences of up to 100 times in electrical conductivity and of 4 times in nonlinear optical activity (NLO) have been measured between 1 and 1′. This compound is one of few displaying multifunctionality, electrical conductivity, NLO, and crystal–crystal stability upon release and recovery of iodine. It is also unique in the iodine release from polyiodide anions in a metal–organic framework.

Capture and reversible storage of volatile iodine by porous carbon with high capacity

“…Recent researches on iodine adsorption and storage have mainly focused on the development of silver-loaded zeolites and various organic solids, including CMPs, MOFs, and POPs [2][3][4][5][6][7][8][9]. Interestingly, we found the iodine adsorption by the KOH-AC was highly efficient.…”

“…Silver-based zeolites, metal-organic frameworks (MOFs), and covalently linked porous organic polymers (POPs) have been developed [2][3][4][5][6][7][8][9][10][11]. For example, Cooper et al described a strategy for efficient removal of iodine vapor using porous organic crystals [12].…”

“…For example, Cooper et al described a strategy for efficient removal of iodine vapor using porous organic crystals [12]. Nenoff and Zeng et al exploited MOFs as a new type of sorbents for efficient iodine capture [3,8,9]. Sigen et al reported a metalloporphyrin-based conjugated microporous polymer (CMP) with exceptional performance in the reversible adsorption of iodine [2].…”

Infinite Polyiodide Chains in the Pyrroloperylene–Iodine Complex: Insights into the Starch–Iodine and Perylene–Iodine Complexes

“…Schroder and co-workers [6] have reviewed the rich structural chemistry that emerges when macrocylic thioethers are employed to stabilize oligomeric iodine chains. Yin et al [7] have reported a metal-organic framework based on Cu II cations and I 5 À and I 7 À chains. Kloo et al [8] have also employed ab-initio techniques to study the structure and stability of short I n À moieties in the vacuum.…”

Inside Back Cover: Infinite Polyiodide Chains in the Pyrroloperylene–Iodine Complex: Insights into the Starch–Iodine and Perylene–Iodine Complexes (Angew. Chem. Int. Ed. 28/2016)

“…Schroder and coworkers 6 have reviewed the rich structural chemistry that emerges when macrocylic thioethers are employed to stabilize oligomeric iodine chains. Yin et al 7 have reported a metal-organic framework based on Cu(II) cations and I5 − and I7 − chains. Kloo et al 8 have also employed ab-initio techniques to study the structure and stability of short In -moieties in the vacuum.…”