The same but different: Four samples of an organic zinc phosphate hybrid material prepared at four different temperatures have the same structure but show distinct luminescence (see pictures of two of the samples).
In the last decade, the synthesis of nanoporous materials with extended network topologies has advanced extensively owing to the increasing demand for functional materials in applications involving molecular recognition, shape-selective catalysis, fluid separation, and hydrogen gas storage.[1] Until now, two major categories of nanoporous structures have been under intense investigation: one with whole inorganic framework, such as silica-based zeolites, germanates, and phosphorous-based metal oxides; and another with organic-inorganic hybrid frameworks; that is, porous coordination polymers [2] and metal-organic frameworks (MOFs).[3] The largest pore and/or channel opening that has been observed in inorganic frameworks are 18-membered rings (18MR) in silicates, [4] 24MR in metal phosphates, [5] 26MR in metal phosphites, [6] and 30MR in germanates. [7] In the hybrid frameworks, however, the cavities were determined from pore structure analysis based upon gas sorption studies. By using bulky organic units to co-construct the framework, even higher porosity or larger pores can be produced. For example, the pore size found in the framework MIL-101 [8] was up to 4.6 nm, and the void space in MOF-177 [9] was reported to increase the size of a unit-cell volume by up to 81 %, thus substantially surpassing the volume of inorganic structures.Exploration of enhanced porosity and even new properties in the inorganic framework have thus been pursued by mediating with organic building units. To date, transforming inorganic frameworks into hybrid frameworks has only been possible in phosphate/phosphite (MPO) systems; few organic molecules are found to be suitable, for example, the smallest oxalate linker and certain polyamine molecules. Encouragingly however, quite a few unique three-dimensional metal oxalatophosphates [10] and pillar-layered organo-metallophosphates (OMPO) [11] have been formed that have extra-large channels with interesting properties. The oxalate-mediated nanoporous gallium phosphates of NTHU-6[10a] or NTHU-7, [10b] with their unprecedented photoluminescence properties, has established a new class of LED color-conversion phosphors. Aryl carboxylates, such as benzene dicarboxylate (bdc) or benzene-1,2,4,5-tetracarboxylate (btec), which are effective organic building units of MOFs or coordination polymers, had not been found to adapt to MPOs until the discovery of (H 2 tmdp)[(ZnHPO 4 ) 2 (bdc)] (tmdp = 4,4'-trimethylenedipyridine; NTHU-2),[11a] the first bdc-mediated OMPO compound, in 2004. This compound has gismondinelike inorganic sheets pillared by bdc to give nanometer-sized channels and a remarkable gas sorption behavior; of vital importance, this sorption revealed bimodal pore-size distributions. To gain a deeper insight into the intriguing and useful porous properties, we have focused on the study of carboxylate-incorporated MPO frameworks. Herein we report the first btec-mediated metal phosphate compound, (Hbpy)-[Zn 2 PO 4 (btec)(Hbpy) 2 ] (bpy = 4,4'-bipyridine), designated NTHU-8. This compound e...
Kleiner Unterschied: Vier Proben eines Zinkphosphat‐Hybridmaterials mit organischen Liganden, die bei vier verschiedenen Temperaturen hergestellt wurden, haben die gleiche Struktur, aber unterschiedliche Lumineszenz (zwei Proben sind abgebildet).
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