阴离子型菱形网状的手性多孔铟金属有机框架合成结构和氮气吸附.docx

1、阴离子型菱形网状的手性多孔铟金属有机框架合成结构和氮气吸附阴离子型菱形网状的手性多孔铟金属有机框架：合成、结构和氮气吸附 doi:10.1039/C1C01 EJu05ly 1120011 E UNIhttVEp:/RSpubITs.rsYoc.on rg| View Online CrystEngComm Dynamic Article Links C Cite this: CrystEngComm, 2011, 13, 4005 www.rsc.org/crystengcomm PAPER A porous chiral In-MOF with anionic-type diamond n

2、etwork: synthesis, structure and nitrogen gas adsorption? Liping Wang, Tianyou Song, Liangliang Huang, Jianing Xu,* Chao Li, Caixia Ji, Liang Shan a and Li Wang* Received 21st January 2011, Accepted 18th March 2011 DOI: 10.1039/c1ce05110e aaabaaa A novel porous chiral In-MOF InH(D-C10H14O4)2 (1) wit

3、h a left-handed helical channel assembled from D-(+)-camphoric acid (D-H2Cam), has been prepared under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the tetragonal space group 3 Z ? 4. The framework feature of compound 1 is characteristic

4、of four-connected anionic-type diamond net with left-handed chiral channel. Moreover, compound 1 exhibits high surface area. P43212 (no. 96) with parameters: a ? 13.8954 A, b ? 13.8954 A, c ? 17.7870 A, V ? 3434.4(7) A , Introduction The design and synthesis of porous metalorganic frameworks (MOFs)

5、with characteristic structural chirality are topics of current 1,2 interest and of great challenge in materials science, not only due to their intriguing structures, but also owing to their potential applications as functional materials for enantioselective catalysis 37 and separation, non-linear op

6、tics, ferroelectrics and magnetism. Recently, the synthesis of chiral low-connectivity (3- or 4-connected) MOFs attracts special attention on accounts of their 8 appealing architectures and high surface areas. To our knowledge, compared with tremendous success in the synthesis of low-connectivity fr

7、amework materials in the past decades, 3D chiral low-connectivity MOFs are still rare. DoPwubnllisoaheded d on by 13 NAAprNil JI20N11 G on pseudo tetrahedral geometry which can be considered as a 4-connected node. We are interested in the design and synthesis of porous chiral MOFs, especially, chira

8、l low-connectivity In-MOFs. The litera-ture studies indicated that one of the most effective and direct approaches to prepare chiral MOFs is to use enantiopure chiral ligands as starting materials which impart homochirality to the 11 resulting crystals. To date, the synthesis of chiral MOFs has achi

9、eved huge success through naturally organic ligands with chiral 12 polycarboxylate groups and polypyridyl groups. Among them, D-camphoric acid (D-H2Cam), as an enantiopure ditopic organic linker, has constructed a variety of chiral MOFs of transition metals, such as M2(D-Cam)2(4,4-bpy)n (M ? Cu, Zn)

10、 containing a homochiral grid-like (4,4) layered structure, Co(D-Cam)1/2(bdc)1/2(tmdpy) exhibiting homochiral topology of quartz dual net and Ni(D-cam)(H2O)2 with homochiral srs topology. Thus we choose D-H2Cam as organic ligand to synthesize the new chiral low-connectivity In-MOF. Finally, a novel

11、anion-type diamond network InH(D-C10H14O4)2 (1) with a left-handed channel was obtained under solvothermal condi-tions. It is noted that the anionic frameworks practically that of chiral anionic MOFs, are still rarely occurred in MOFs, even this phenomenon is very common in zeolites, phosphates and

12、other oxides. Herein, we describe the synthesis, crystal structure and characterization of compound 1, along with nitrogen gas absorption property. 13 More recently, In-MOFs continue to receive much attention due to their flexible coordination characteristics (six, seven and eight) and exceptional g

13、as absorption and catalytic property used as 8c,9 heterogeneous Lewis acid catalysts in organic trans-formations. Furthermore, In-MOFs can be a more attractive choice in the design of low-connectivity and high surface area MOFs because of its eight-coordinate central building block with four equival

14、ent 10 carboxylate ligands. For example, in quartz-like chiral InH(BDC)2, the indium centers adopt triangulated dodecahedral geometries by the chelation of four carboxylate groups from four terephthalate anions to form a highly distorted a College of Chemistry, Jilin University, Changchun 130012, Ji

15、lin, P. R. China. E-mail: lwang99; Fax: +86-431-85671974; Tel: + 86- 431-85168471 b State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, Jilin, P. R. China. E-mail: xujn; Fax: +86-431-85671974; Tel: + 86-431- Experimental

16、Materials and measurements 85168471 ? Electronic supplementary information (ESI) available: Details of the structure information, PXRD, IR and TGA of compound 1. CCDC reference number 808780. For ESI and crystallographic data in CIF or All chemicals were obtained from commercial sources and used wit

17、hout further purification. Powder X-ray diffraction (PXRD) data were obtained using SHIMADAZU XRD-6000 diffrac- tometer with Cu-Ka radiation (l ? 1.5418 A), with the step size CrystEngComm, 2011, 13, 40054009 | 4005 other electronic format see DOI: 10.1039/c1ce05110e This journal is a The Royal Soci

18、ety of Chemistry 2011 doi:10.1039/C1C01 EJu05ly 1120011 E DowPnluboalisdehed d by on N13 AANprJIil N20G 11 Uon NhtItpV:/EpuRbsSI.rsTc.Y oron g | View Online and the count time of 0.02 and 4 s, respectively. The elemental analysis was conducted on a Perkin Elmer 2400 elemental analyzer. ICP-AES (indu

19、ctively coupled plasma-atomic emission spectroscope) analysis was performed on a Perkin Elmer Optima 3300DV ICP instrument. FTIR spectrum was recorded on 1 a Nicolet Impact 410 spectrometer between 4000 and 400 cm Space group a/A using the KBr pellet method. Thermogravimetric analysis (TGA) was cond

20、ucted on a Perkin-Elmer TGA 7 thermogravimetric b/A c/A analyzer with a heating rate of 10 C min from room temper- ature to 800 C. Gas sorption experiment was carried out with a Micrometrics ASAP 2020 instrument. 1 R(F) Nets Flack a P43212 13.8954(15) 13.8954(15) 17.787(2) 0.0658 b 0.16(10) P43212 1

21、3.7393(1) 13.7393(1) 37.2281(5) 0.0798 Dia Ths 0.03(7) P43212 13.7548(2) 13.7548(2) 38.1612(8) 0.0767 0.02(8) Ths Synthesis of InH(D-C10H14O4)2 (1) All reagents were of analytical grade. Compound 1 was solvothermally prepared from a starting mixture containing indium trichloride (InCl3), D-(+)-camph

22、oric acid (D-H2Cam), ethylenediamine anhydrous (EDA) and N,N-dimethylforma- mide (DMF). Indium trichloride was obtained hydrothermally by direct reaction of In2O3 with HCl at 180 C for 2 d under autogenous pressure. The molar ratio of the initial mixture was InCl3 : D-H2Cam : EDA : DMF ? 1 : 2 : 6 :

23、 362 . The mixture was further stirred for one hour at room temperature and heated at 100 C for 3 d in a 23 mL Teflon-lined stainless steel autoclave (filled up to 30% volume capacity), then slowly cooled down to the ambient temperature. Colourless block crystals of compound 1 were collected by filt

24、ration, washed with DMF and air-dried. The yield of product was 57% in weight based on indium. In order to check the phase purity of the products, powder X-ray diffraction (PXRD) experiments have been carried out for the compound 1 (Fig. S1?). The agreement between the experimental and simulated pow

25、der X-ray diffraction patterns indicated the phase purity of the as-synthesized product. The differences in intensity may be owing to the preferred orientation of the powder samples. The ICP and elemental analysis: found (wt %) In 17.05, C 46.25, H 6.23, N 4.00; calcd (wt %) In 16.97; C 46.13, H 6.6

26、5, N 4.14. IR spectrum (KBr/cm ): 3452 (br), 2966 (w), 2455 (br), 2067 (w), 1639 (s), 1564 (vs), 1415 (s), 1130 (vs), 848 (m), 541 (m). ? D-camphoric acid, EMIm ? 1-ethyl-3-methyl imidazolium, b BMIm ? 1-butyl-3-metyl imidazolium. Dia ? diamond, Ths ? ThSi2 topology. D-H2cam Table 1, while the selec

27、ted bond lengths and angles are presented in Table S1?. Gas sorption measurement Before the measurement, the sample of 1 was soaked in methanol for 3 d to remove DMF and H2O solvent molecules, then filtrated, and dried at room temperature. Then, the sample was 5 pretreated under high vacuum (less th

28、an 10 Torr) at 80 C overnight to remove methanol and all residue solvents in the channels. About 100 mg of the desolvated sample was used for the entire adsorption measurement. Results and discussion Structural description that 1 Flack A single-crystal X-ray diffraction analysis indicates crystalliz

29、es in a chiral P43212 space group, with the 1 parameter of 0.16(10). As shown in Fig. 1, the asymmetric unit of the compound 1 contains one crystallographically indepen- dent In(III) ion. Each In(III) ion is eight coordinated by eight carboxylate oxygen atoms from four D-Cam ligands to form a dodeca

30、hedral motif, which exhibits high coordinating ability of main group elements. InO distances and OInO bond angles are ranging from 2.219(9) to 2.392(8) A and 56.1(3) to 164.1(3) , respectively, which are always observed for other Single-crystal X-ray crystallography A suitable single crystal of comp

31、ound 1 (0.1 0.1 0.1 mm) was selected for single-crystal X-ray diffraction analysis. The intensity data were collected on a Siemens Smart CCD diffrac- 3 In(III)- carboxylate frameworks. The two carboxylate oxygen atoms of 16 tometer with graphite-monochromated Mo-Ka (l ? 0.71073 A) radiation at a tem

32、perature of 293(2) K. No significant decay was observed during the data collection. Data processing was accomplished with the RAPID AUTO processing program. The structure was solved by direct method and refined by full-matrix 2 least-squares on F using the SHELXTL crystallographic soft- 14,15 ware package. All the indium atoms were located first, and then the oxygen and carbon atoms were subsequently found in difference Fourier