Journal of Guangxi Normal University(Natural Science Edition) ›› 2012, Vol. 30 ›› Issue (3): 171-177.

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Rigid Pillars and Double Walls in a Porous Metal-Organic Framework: Single-Crystal to Single-Crystal,Controlled Uptake and Release of Iodine and Electrical Conductivity

ZENG Ming-hua, LI Dan-dan, YIN Zheng, WANG Qiang-xin, ZHANG Dong-cai   

  1. College of Chemistry and Chemical Engineering,Guangxi Normal University,Guilin Guangxi 541004,China
  • Received:2012-06-20 Online:2012-09-20 Published:2018-12-04

Abstract: The first high stable micro-porous metal-organic framework with rigidpillars and double-walls,Zn3(pybz)2(lac)2·2.5DMF (1) wasconstructed from infinite pillars {[Zn3(DL-lac)2]2+}n and 4-pyridyl benzoate(pybz) which is long,polar and ditopic at the opposite ends through the pyridine and the carboxylate under solvothermal reaction.1 crystallized in tetragonal P4—21c space group.Thereare 1D channels running along the c axis with window size of 1.12×1.02 nm2 in 1.A void volume of 43.5% was calculated by PLATON.A Langmuir surface area of918.5 m2·g-1 further confirms the permanent porosity of complex 1′.The framework of 1 is highly stable up to 400 °C which is confirmed by TG and variable temperature powder X-ray diffraction measurement.Guest removed phase Zn3(pybz)2(lac)2 (1′) can be obtained through single-crystal to single-crystal transformation.1′ shows outstanding iodine enrichment ability in cyclohexanesolution of I2and one gram of 1′ can absorb approximately 1 g of iodine to obtain {[Zn3(pybz)2(lac)2]·3I2}n (1′·3I2).1′·3I2 shows controlled iodine releasing in ethanol solvent.The potential intermolecular interactions between I2 and π-electronwalls induced n→σ* charge-transfer and resulted in cooperative electrical conductivity for of 1′ 3I2,which is about 440 times higher than iodine.A special phenomena was found that increased electrical conductivityresulted from cooperative interaction between insulating guests and insulating coordination polymers for the first time.

Key words: metal-organic framework, single-crystal to single-crystal transformation, iodine enrichment and controlled releasing of iodine, cooperative electrical conductivity

CLC Number: 

  • O641
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