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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/cm070553+ ; [EN] Layered organic-inorganic hybrid materials were synthesized by pillaring with viologen and nitroaniline compounds which are intercalated between magadiite layers. The bridged silsesquioxanes, 4,4'-bis(trimethoxysilylpropyl)viologen and 4-nitro-N,N'-bis(3-trimethoxysilyl)propylaniline react with the surface silanol groups of the inorganic layers of silicate, bonding covalently with them. The preparation process was followed by DRX, and the pillarization was corroborated using chemical and thermogravimetrical analyses. The presence of viologen and nitroaniline organic linkers covalently bonded to inorganic layers was confirmed by C-13 and Si-29 NMR spectroscopy. UV-visible diffuse reflectance permitted to observe the high stabilization achieved by the intercalated organic fragments. Micro- and mesoporosity were also generated because of the existence of interlayer galleries conformed by homogenously distributed organic linkers into the interlayer space. The layered organic-inorganic hybrids exhibited a thermally stable network, and the organic spacers remained after elimination of the swelling agents by acid extraction. The resultant materials can be of interest as sensors and for nonlinear optics. ; Financial support by the Spanish Government (MAT-2006-14274-C02-01 and MAT2006-26599-E) and Universidad Polite´cnica de Valencia (PPI-06-05) is gratefully acknowledged. ; Díaz Morales, UM.; Cantin Sanz, A.; Corma Canós, A. (2007). Novel layered organic-inorganic hybrid materirals with bridged silsesquioxanes as Pillars. Chemistry of Materials. 19(15):3686-3693. https://doi.org/10.1021/cm070553+ ; S ; 3686 ; 3693 ; 19 ; 15

[EN] By using a Diels-Alder (DA) reaction as a base case, we show that a pure silica zeolite acting as an entropy-trapping scaffold can be synthesized with an organic structure directing agent (OSDA) analogue of the transition state (TS) of the DA reaction. A cavity stabilization of the TS is observed with the corresponding decrease in the activation energy of the reaction. A lower enthalpy of activation and a larger decrease in entropy are obtained with the zeolite synthesized with the analogue of the DA TS when compared with other zeolitic structures. Those differences are maintained, while catalytic activity is increased, when active sites are introduced in the zeolite. The catalytic zeolitic system synthesized with the OSDA analogue of the TS shows conceptual similarities with "de novo design" of an artificial enzyme to perform DA reactions, in where a suitable scaffold of existing proteins is chosen, and computationally designed active sites able to catalyze the cycloaddition reaction are introduced. ; This work has been supported by the European Union through ERC-AdG-2014-671093 (SynCatMatch), by the Spanish Government-MINECO through "Severo Ochoa" (SEV-2016-0683) and RTI2018-101033, and by La Caixa Foundation through MITSPAIN SEED FUND (LCF/PR/MIT17/11820002). Eva M. Gallego acknowledges "La Caixa -Severo Ochoa" International PhD Fellowships (call 2015). The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization. ; Gallego-Sánchez, EM.; Paris, C.; Cantin Sanz, A.; Moliner Marin, M.; Corma Canós, A. (2019). Conceptual similarities between zeolites and artificial enzymes. Chemical Science. 10(34):8009-8015. https://doi.org/10.1039/C9SC02477H ; S ; 8009 ; 8015 ; 10 ; 34 ; Woodward, R. B., Sondheimer, F., Taub, D., Heusler, K., & McLamore, W. M. (1952). The Total Synthesis of Steroids1. Journal of the American Chemical Society, 74(17), 4223-4251. doi:10.1021/ja01137a001 ; Woodward, R. B., Bader, F. E., Bickel, H., Frey, A. J., & Kierstead, R. W. (1956). THE ...

[EN] A multinuclear NMR has been carried out to elucidate the mechanism of action of CC3-R box-type chiral materials for the separation of enantiomers, supported by theoretical calculations. The potential of these materials to be used as chiral resolution agents through NMR is evidence in this study. ; Program Severo Ochoa SEV-2016-0683 is gratefully acknowledged. S.S-F. thanks MEC for his Severo Ochoa Grant SPV-2013-067884, P.O.-B. thanks MEC for his Ramon y Cajal contract RYC-2014-16620. M.B. and F.R. thank the financial support by the Spanish Government (MAT2017-82288-C2-1-P and MAT2015-71842-P). The authors thank the MULTY2-HYCAT (EU-Horizon 2020 funded project under grant agreement no. 720783). The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization. ; Saez-Ferre, S.; Boronat Zaragoza, M.; Cantin Sanz, A.; Rey Garcia, F.; Oña-Burgos, P. (2018). Elucidation of the Interaction Mechanism between Organic Chiral Cages with Biomolecules through Nuclear Magnetic Resonance and Theoretical Studies. The Journal of Physical Chemistry C. 122(29):16821-16829. https://doi.org/10.1021/acs.jpcc.8b05069 ; S ; 16821 ; 16829 ; 122 ; 29

A new zeolite (named as ITQ-52) having large cavities and small and medium channels has been synthesized. This was achieved by using a new family of amino-phosphonium cations as organic structure directing agents (OSDA). These cations contain P−C and P−N bonds, and therefore they lie between previously reported P-containing OSDA, such as tetraalkylphosphonium and phosphazenes. In this study, it has been found that 1,4- butanediylbis[tris(dimethylamino)]phosphonium dication is a very efficient OSDA for crystallization of several zeolites, and in some particular conditions, the new zeolite ITQ-52 was synthesized as a pure phase. The structure of ITQ-52 has been solved using high-resolution synchrotron X-ray powder diffraction data of the calcined solid. This new zeolite crystallizes in the space group I2/m, with cell parameters a = 17.511 Å, b = 17.907 Å, c = 12.367 Å, and β = 90.22°. The topology of ITQ-52 can be described as a replication of a composite building unit with ring notation [435461] that gives rise to the formation of an interconnected 8R and 10R channel system. ; We thank financial support by the Spanish Government (MAT2012-38567-C02-01, MAT2012-38567-C02-02, Consolider Ingenio 2010-Multicat CSD-2009-00050 and Severo Ochoa SEV-2012-0267). R.S. acknowledges to UPV for a FPI predoctoral fellowship. Authors thank ALBA Light Source for beam allocation at beamline MSPD. We thank G. Sastre and J. A. Vidal for computational calculations and MAS NMR experiments, respectively. ; Simancas Coloma, R.; Jorda Moret, JL.; Rey Garcia, F.; Corma Canós, A.; Cantin Sanz, A.; Peral, I.; Popescu, C. (2014). A new microporous zeolitic silicoborate (ITQ-52) with interconnected small and medium pores. Journal of the American Chemical Society. 136(9):3342-3345. doi:10.1021/ja411915c ; S ; 3342 ; 3345 ; 136 ; 9

[EN] A new germanosilicate zeolite (denoted as ITQ-53) with extra-large pores has been synthesised using tri-tertbutylmethylphosphonium cation as the organic structure directing agent (OSDA). Rotation electron diffraction (RED) was used to identify ITQ-53 from an initially-synthesised sample containing impurities, and to solve its structure. The structure was refined against PXRD data of pure ITQ-53 samples obtained after synthesis optimisation. ITQ-53 is the first example of extra-large pore zeolites with tri-directional interconnected 14 x 14 x 14-ring channels. It is stable up to at least 650 degrees C. The structure of ITQ-53 changes from monoclinic to orthorhombic upon calcination. ; This work was supported by the Spanish Government (MAT2012-38567-C02-01, Consolider Ingenio 2010-Multicat CSD-2009-00050 and Severo Ochoa SEV-2012-0267), the Swedish Research Council (VR), the Swedish Governmental Agency for Innovation Systems (VINNOVA) and the Knut & Alice Wallenberg Foundation through a grant for purchasing the TEMs and the project grant 3DEM-NATUR. Yifeng Yun thanks the China Scholarship Council (CSC). ; Yun, Y.; Hernández Rodríguez, M.; Wan, W.; Zou, X.; Jorda Moret, JL.; Cantin Sanz, A.; Rey Garcia, F. (2015). The first zeolite with a tri-directional extra-large 14-ring pore system derived using a phosphonium-based organic molecule. Chemical Communications. 51(36):7602-7605. https://doi.org/10.1039/c4cc10317c ; S ; 7602 ; 7605 ; 51 ; 36 ; C. Baerlocher and L.McCusker, Database of Zeolite Structures: http://www.iza-structure.org/databases/ ; Estermann, M., McCusker, L. B., Baerlocher, C., Merrouche, A., & Kessler, H. (1991). A synthetic gallophosphate molecular sieve with a 20-tetrahedral-atom pore opening. Nature, 352(6333), 320-323. doi:10.1038/352320a0 ; Su, J., Wang, Y., Lin, J., Liang, J., Sun, J., & Zou, X. (2013). A silicogermanate with 20-ring channels directed by a simple quaternary ammonium cation. Dalton Trans., 42(5), 1360-1363. doi:10.1039/c2dt32231e ; Wei, Y., Tian, Z., Gies, H., ...

[EN] The synthesis of crystalline molecular sieves with pore dimensions that fill the gap between microporous and mesoporous materials is a matter of fundamental and industrial interest(1-3). The preparation of zeolitic materials with extralarge pores and chiral frameworks would permit many new applications. Two important steps in this direction include the synthesis(4) of ITQ-33, a stable zeolite with 18 x 10 x 10 ring windows, and the synthesis(5) of SU-32, which has an intrinsically chiral zeolite structure and where each crystal exhibits only one handedness. Here we present a germanosilicate zeolite (ITQ-37) with extralarge 30-ring windows. Its structure was determined by combining selected area electron diffraction ( SAED) and powder X-ray diffraction (PXRD) in a charge-flipping algorithm(6). The framework follows the SrSi2 (srs) minimal net(7) and forms two unique cavities, each of which is connected to three other cavities to form a gyroidal channel system. These cavities comprise the enantiomorphous srs net of the framework. ITQ-37 is the first chiral zeolite with one single gyroidal channel. It has the lowest framework density (10.3 T atoms per 1,000 angstrom(3)) of all existing 4-coordinated crystalline oxide frameworks, and the pore volume of the corresponding silica polymorph would be 0.38 cm(3) g(-1). ; This project is supported by the CICYT ( Project MAT 2006-14274-C02-01 and Prometeo 2008 GV), the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA). J.S. and C. B. are supported by post-doctoral grants from the Carl-Trygger and Wenner-Gren foundations respectively. M. M. thanks ITQ for a scholarship. ; Sun, J.; Bonneau, C.; Cantin Sanz, A.; Corma Canós, A.; Díaz Cabañas, MJ.; Moliner Marin, M.; Zhang, D. (2009). ITQ-37 a chiral zeolite framework following the SrSi2 net and containing 30-ring extra-large gyroidal channels. Nature. 458(7242):1154-1158. https://doi.org/10.1038/nature07957 ; S ; 1154 ; 1158 ; 458 ; 7242 ; Davis, M. E. Ordered porous ...

[EN] It was found that either polymorph B or polymorph C of zeolite beta can be obtained from the same structure directing agent: 4,4-dimethyl-4-azonia-tricyclo[5.2.2.0(2,6)] undec-8-ene hydroxide. The synthesis occurs through a consecutive process where polymorph B is first formed and then transformed into polymorph C. It is possible to produce a zeolite highly enriched in polymorph B, provided that the transformation of this phase into polymorph C is slowed down up to the point where polymorph C is only detected at trace levels. The structure of polymorph B was determined for the first time by electron crystallography with SAED and HRTEM from areas of unfaulted polymorph B crystals. ; Financial support from the Spanish Government (Project MAT2006-14274-C02–01) and the EU Commission (TOPCOMBI Project) is gratefully acknowledged. M.M. thanks CSIC for an I3P grant. J.S. is supported by a postdoctoral grant from the Carl Trygger Foundation. The Berzelii Centre EXSELENT is supported by the Swedish Research Council (VR) and the Swedish Governmental Agency for Innovation Systems (VINNOVA). ; Corma Canós, A.; Moliner Marin, M.; Cantin Sanz, A.; Díaz Cabañas, MJ.; Jorda Moret, JL.; Zhang, D.; Sun, J. (2008). Synthesis and structure of polymorph B of zeolite Beta. Chemistry of Materials. 20(9):3218-3223. doi:10.1021/cm8002244 ; S ; 3218 ; 3223 ; 20 ; 9

2122 2125 54 17 ; S Ch. Baerlocher , A.Hepp and W. M.Meier , DLS-76. Distance least squares refinement program , ETH Zurich Institut fur Kristallographie , Zurich, Switzerland , 1977 ; Sun, J., Bonneau, C., Cantín, Á., Corma, A., Díaz-Cabañas, M. J., Moliner, M., … Zou, X. (2009). The ITQ-37 mesoporous chiral zeolite. Nature, 458(7242), 1154-1157. doi:10.1038/nature07957 ; [EN] Here, we present the synthesis and structure determination of the new zeolite ITQ-62. Its structure was determined via ultra-fast electron diffraction tomography and refined using powder XRD data of the calcined material. This new zeolite contains a tridirectional channel system of highly distorted 8-rings, as well as a monodirectional 12-ring channel system. The authors gratefully acknowledge financial support from the Spanish Government (MAT2015-71842-P and MAT2015-71261-R MINECO/FEDER and Severo Ochoa SEV-2016-0683). The authors thank ALBA Light Source for beam allocation at the beamline MSPD, and specially thank the Electron Microscopy Service of the Universitat Politecnica de Valencia. Finally, the authors thank Dr Alejandro Vidal and Dr Teresa Blasco for helping in the NMR data discussion. Bieseki, L.; Simancas Coloma, R.; Jorda Moret, JL.; Bereciartua-Pérez, PJ.; Cantin Sanz, A.; Simancas-Coloma, J.; Pergher, SB. (2018). Synthesis and structure determination via ultra-fast electron diffraction of the new microporous zeolitic germanosilicate ITQ-62. Chemical Communications. 54(17):2122-2125. https://doi.org/10.1039/c7cc09240g Barrer, R. M., & Denny, P. J. (1961). 201. Hydrothermal chemistry of the silicates. Part IX. Nitrogenous aluminosilicates. Journal of the Chemical Society (Resumed), 971. doi:10.1039/jr9610000971 Kerr, G. T. (1966). Chemistry of Crystalline Aluminosilicates. II. The Synthesis and Properties of Zeolite ZK-4. Inorganic Chemistry, 5(9), 1537-1539. doi:10.1021/ic50043a015 Burton, A. W., & Zones, S. I. (2007). Organic Molecules in Zeolite Synthesis: Their Preparation and Structure-Directing Effects. ...

[EN] Here, we present the synthesis and structure determination of the new zeolite ITQ-62. Its structure was determined via ultra-fast electron diffraction tomography and refined using powder XRD data of the calcined material. This new zeolite contains a tridirectional channel system of highly distorted 8-rings, as well as a monodirectional 12-ring channel system. ; The authors gratefully acknowledge financial support from the Spanish Government (MAT2015-71842-P and MAT2015-71261-R MINECO/FEDER and Severo Ochoa SEV-2016-0683). The authors thank ALBA Light Source for beam allocation at the beamline MSPD, and specially thank the Electron Microscopy Service of the Universitat Politecnica de Valencia. Finally, the authors thank Dr Alejandro Vidal and Dr Teresa Blasco for helping in the NMR data discussion. ; Bieseki, L.; Simancas Coloma, R.; Jorda Moret, JL.; Bereciartua-Pérez, PJ.; Cantin Sanz, A.; Simancas-Coloma, J.; Pergher, SB. (2018). Synthesis and structure determination via ultra-fast electron diffraction of the new microporous zeolitic germanosilicate ITQ-62. Chemical Communications. 54(17):2122-2125. https://doi.org/10.1039/c7cc09240g ; S ; 2122 ; 2125 ; 54 ; 17 ; Barrer, R. M., & Denny, P. J. (1961). 201. Hydrothermal chemistry of the silicates. Part IX. Nitrogenous aluminosilicates. Journal of the Chemical Society (Resumed), 971. doi:10.1039/jr9610000971 ; Kerr, G. T. (1966). Chemistry of Crystalline Aluminosilicates. II. The Synthesis and Properties of Zeolite ZK-4. Inorganic Chemistry, 5(9), 1537-1539. doi:10.1021/ic50043a015 ; Burton, A. W., & Zones, S. I. (2007). Organic Molecules in Zeolite Synthesis: Their Preparation and Structure-Directing Effects. Introduction to Zeolite Science and Practice, 137-179. doi:10.1016/s0167-2991(07)80793-2 ; Zones, S. I., Nakagawa, Y., Lee, G. S., Chen, C. Y., & Yuen, L. T. (1998). Searching for new high silica zeolites through a synergy of organic templates and novel inorganic conditions. Microporous and Mesoporous Materials, 21(4-6), 199-211. ...