Health & Environmental Research Online (HERO)


Print Feedback Export to File
4272391 
Journal Article 
Versatile Tailoring of NH2-Containing Metal-Organic Frameworks with Paddle-Wheel Units 
Guo, XG; Zhang, ZY; Qiu, S; Su, X; Wang, YB; Sun, X 
2017 
Yes 
Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765 
23 
70 
17727-17733 
English 
29027280 
WOS:000418075600017 
An amine-containing non-interpenetrating pillar-layer framework, [Zn2(dbtcb)(L1)]⋅x solvent (1), has been synthesized from Zn(NO3)2and the ligands 1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzene (H4DBTCB) and 2,5-bis(4-pyridyl)aniline (L1). The [Zn2(COO)4] secondary building units (SBUs) are bridged by DBTCB to form two-dimensional layers that are linked by L1 ligands acting as pillars to form a three-dimensional network. This NH2-containing framework can undergo versatile tailoring through post-synthetic covalent modification, solvent-assisted linker exchange (SALE), and single-crystal-to-single-crystal (SC-SC) transmetalation reactions. Acetamide-functionalized [Zn2(L2)(dbtcb)]⋅xsolvent (2) could be obtained by direct synthesis from Zn(NO3)2, N-acetyl-2,5-bis(4-pyridyl)aniline (L2) and H4DBTCB. Importantly, compound 1 with pure NH2ligands as pillars could be obtained by SALE of 2 with L1 in DMSO solution. The transmetalation reactions of 1 with CuII, NiII, and CoIIwere studied; inductively coupled plasma-atomic emission (ICP) analysis revealed that 1 underwent almost complete SC-SC transmetalation with CuIIwithin 30 h, whereas with NiIIand CoIIonly 70 and 80 % substitutions were achieved. Photoluminescence studies revealed that 1 and 2 display yellow-green and UV emission, respectively, under a UV lamp. Furthermore, the photoluminescent properties could be tuned by introducing mixed pillar amino ligands L1 and L2 into the MOF to produce multivariate (MTV) MOF 3 displaying overall orange emission. 
Chemistry; Photons; Metal-organic frameworks; Single crystals; Benzene; Ligands; Emission analysis; Aniline; Pillars; Emissions; Photoluminescence; Inductively coupled plasma