Since their discovery, microporous materials have been broadly exploited as shape-selective catalysts and sorbents in different research fields, 1 accompanied by an ongoing search for novel molecular sieve structures and new synthesis methods. For example, Morris and co-workers have recently developed a novel method (ionothermal synthesis) for preparing molecular sieves, which involves the use of ionic liquid as both the solvent and structuredirecting agent. 2 By using this method, Morris et al. have prepared several aluminophosphate and cobalt aluminophosphate structures in an imidazolium-based ionic liquid (1-ethyl-3-methylimidazolium bromide ([emim]Br)). Compared with the traditional hydrothermal or solvothermal methods, 1,3 preparations using the ionothermal method can take place at or near ambient pressure because of the negligible vapor pressure of ionic liquids. 4 This eliminates safety concerns associated with high pressures.The synthesis of molecular sieves often requires the addition of organic molecules, such as amines and quaternary ammonium ions, into the synthesis mixture. The role of these molecules has been described as a structure-directing effect, referring to the complementary shapes of the structure-directing agents and the frameworks they direct. Normally the addition of structure-directing agents to molecular sieve synthesis can affect the rate at which a particular structure is formed. In this work, we report the study of the structure-directing role of amines in the ionothermal synthesis of molecular sieves in 1-butyl-3-methylimidazolium bromide ionic liquid ([bmim]Br). 5 We show that the original crystallization process can be altered by the addition of amine, as summarized in Scheme 1.In the absence of amine, AlPO 4 -11 molecular sieves (AEL-type structure) 6 with minor AlPO 4 -5 (AFI-type structure) 7 were formed after a short induction period at a temperature between 190 and 280°C in [bmim]Br ( Figure 1a and Table 1). Increasing the crystallization time leads to further growth of the AEL structure, while the amount of the AFI structure passed through a maximum and eventually disappeared after 4 h. Both of the two structures are composed of straight one-dimensional channels with AFI containing 12-membered ring (MR) pores (7.3 × 7.3 Å in size) and AEL containing 10-MR pores (6.5 × 4.0 Å). To date, the only ionic liquid used in ionothermal synthesis was [emim]Br. The pore sizes of all the AlPO and CoAlPO products synthesized ionothermally in [emim]Br are no larger than 10-MR. 2,8 The fact that the 12-MR large-pore AFI structure was formed when [bmim]Br was used as the reaction media instead of [emim]Br suggests the possible structure-directing effect of ionic liquid. ( 13 C CP-MAS NMR indicates that the cation of [bmim]Br is occluded in the pores of AlPOs; see Supporting Information.) Moreover, the cation of ionic liquid may have the major influence on the frameworks it directs. Nevertheless, it seems that [bmim] + is still suitable for filling the 10-MR channels because the AEL structu...

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5 Porphyrin-based organic polymer [(Por)OP] was prepared with a most convenient and simple method by condensation of pyrrole and terephthaldehyde in propanoic acid. A direct metallation of (Por)OP with metal acetate led to the formation of the corresponding metalloporphyrin-based organic polymer [M(Por)OP, (M = Zn, Co)]. The M(Por)OP bears dense catalytic sites of metalloporphyrin covalently linked in the skeleton and shows excellent catalytic performance toward cycloaddition of carbon dioxide 10 (CO2) to propylene oxide (PO) to give cyclic propylene carbonate (PC). All of the M(Por)OP-promoted cycloaddition reactions displayed remarkable selectivity to the cyclic carbonate without polycarbonate and other by-products. The effects of various reaction parameters on the catalytic performance of M(Por)OP were investigated systematically in terms of both PC yield and turnover frequency. Moreover, owing to the covalent linkages between catalytic sites of metalloporphyrin in the frameworks, the 15 developed M(Por)OP is stable and insoluble in any commonly used organic solvents and behaves as heterogeneous catalysts in CO2 fixation. Also, the M(Por)OP can be readily separated from the product and reused.75