A Gallogermanate Zeolite with Eleven‐Membered‐Ring Channels

摘要: Zeolites are crystalline microporous materials composed of corner-sharing TO4 (T= Si, Al, P, etc.) tetrahedra, and widely applied in the fields catalysis, ion-exchange, adsorption, separation. So far, 206 types zeolite frameworks have been identified by Structure Commission International Zeolite Association (IZA-SC). The importance increasing number applications for zeolites drives development new materials. Germanate-based particular interest because their rich structural diversity favored larger T O distances smaller T-O-Tangles Ge atoms compared with those Si silicate zeolites. Such geometric factors an important effect on formation small rings, such as double four-membered rings (D4Rs), which believed to be beneficial structures very low framework density (FD), proposed Brunner Meier. Notably, a series D4R-containing germanosilicate extra-large pores has successfully synthesized, ITQ-33 (18 10 ring), ITQ-43 (28 12 ITQ-44 (IRR, 18 ITQ-37 (-ITV) 30-membered-ring windows. In addition, several novel germanate-based built that incorporate trivalent elements, B, Ga, discovered. gallogermanate GeGaO-CJ63 (JST) is constructed exclusively from 3-membered-ring units, structure features pair chiral cages induced metal-complex templates. pore characteristics dimension size may fundamentally affect shapeselective property regards molecular sieving hydrocarbon transformations, can lead or improved separation catalytic processes. Compared even-numbered openings, odd-numbered openings much less frequently observed existing Until now, largest channel 15-membered-ring found ITQ-40. To best our knowledge, there no possesses bordered eleven tetrahedrally coordinated atoms. Herein, we present synthesis characterization j (Ni(C3H10N2)3)36Ni4.7 [Ga81.4Ge206.6O576] (denoted GaGeOJU64, C3H10N2= 1,2-PDA= 1,2-diaminopropane). It exhibits four-connected three-dimensional intersecting 11-membered-ring system. [3.4.6.11] cavities exist pairs enantiomers either containing being surrounded metal complexes used GaGeO-JU64 lowest (FD= 9.9 T/ 1000 ) ever achieved oxide was prepared hydrothermal reaction mixture GeO2, Ga(NO3)3, Ni(CH3COO)2·4H2O, 1,2PDA, H2O molar ratio 1.00:0.39:0.24:19.17:36.76 at 180 8C 8 days Teflon-lined stainless steel autoclave. Themetal complex cation [Ni(1,2-PDA)3] 2+ formed above reaction. obtained pink cubic crystals were washed deionized water dried air. phase purity confirmed agreement between experimental powder X-ray diffraction (XRD) pattern simulated one based analysis (see Supporting Information, Figure S1). XRD patterns sample recorded different temperatures shown S2 Information. crystallizes R 3 space group (No. 148) a= 30.0117(12) , c= 37.301(3) . Its (T=Ge, Ga) forming anionic [T288O576]n 81.4n open framework, 288 sites occupied both 206.6 81.4 Ga difficult distinguish each other (See Experimental Section). negative charges compensated 36 cations void 4.7 Ni trapped six-membered (D6Rs). Ge/Ga/Ni about 5:2:1, energy-dispersive (EDX) results. asymmetric unit contains 16 unique atom positions 4 positions. range 1.724(8)–1.799(7) average bond length 1.76 lies ideal (1.74 (1.82 ). All 119.3(5)–131.8(5)8, reasonable Ge-O-Ga Ge-O-Ge angles. described combination characteristic building units including single (D6Rs), spiro-5 units. D6Rs connected alternately form layer windows (Figure 1a). Further connection these layers results 11membered-ring channels along three directions 1b). free diameters 5.1 7.0 5.2 7.2 5.3 6.8 2 (calculated atomic coordinates van der Waals [*] Y. Xu, Dr. Li, Han, X. Song, Prof. J. Yu State Key Laboraty Inorganic Synthesis Preparative Chemistry College Chemistry, Jilin University Changchun 130012 (P. R. China) E-mail: jihong@jlu.edu.cn