Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 5, Pages 2107-2116Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201404709
Keywords
crystal engineering; fluorescent probes; host-guest systems; manganese; tetradentate ligands
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Funding
- NSFC [21471113]
- Tianjin Educational Committee [20140506]
- Middle-Aged and Young Teachers' Academic Innovation Promotion Project
- Natural Science Foundation of Tianjin [11JCYBJC03600, 14JCQNJC05900]
- Young Scientist Fund [21301128]
- Program for Innovative Research Team in the University of Tianjin [TD12-5038]
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For the purpose of investigating the coordination behavior of sterically congested alkenes and exploring the possibility of cofacial complexation in the polycyclic aromatic system for the formation of extended polymeric networks, a new tetradentate ligand, 1,1,2,2-tetrakis[4-(1H-1,2,4-triazol-1-yl)phenyl]ethylene (TTPE), has been designed and synthesized. By using TTPE as a building block with regard to the self-assembly with MnCl(2 center dot)4H(2)O, a novel two-dimensional coordination framework {[Mn(TTPE)Cl-2]center dot 4CHCl(3)}(n) (1) can be isolated. Anion-exchange and organic-group-functionalized aromatic guest TTPE-loaded host-guest complex experimental results indicate that coordinated Cl- anions in the 2D framework of 1 can be completely replaced with dissociative ClO4- groups in an irreversible single-crystal-to-single-crystal transformation fashion, as evidenced by the anion-exchange products of {[Mn(TTPE)(H2O)(2)](ClO4)(2)center dot 0.5 TTPE center dot 5.25H(2)O}(n) (2). Interestingly, TTPE, acting as an organic template, was encapsulated in the confined space of the 2D grid of 2. To the best of our knowledge, such large organic molecules encapsulated in the reactive organic-group-functionalized aromatic-guest-loaded host-guest complex are unprecedented up to now. Luminescence measurements illustrate that 1 and 2 represent novel examples of sensing materials based on triazole derivatives. Further, 2 has been demonstrated by tuning the fluorescence response of porous metal-organic frameworks as a function of adsorbed small analytes.
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