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71.
Probing the Redox Chemistry of Titanium Silicalite‐1: Formation of Tetrahedral Ti3+ Centers by Reaction with Triethylaluminum
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Elena Morra Prof. Elio Giamello Prof. Mario Chiesa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7381-7388
Transition‐metal ions with open‐shell configurations hold promise in the development of novel coordination chemistry and potentially unprecedented redox catalysis. Framework‐substituted Ti3+ ions with tetrahedral coordination are generated by reductive activation of titanium silicalite‐1 with triethylaluminum, an indispensable co‐catalyst for heterogeneous Ziegler–Natta polymerization catalysts. Continuous‐wave and pulse electron paramagnetic resonance methods are applied to unravel details on the local environment of the reduced transition metal‐ions, which are shown to be part of the silica framework by detection of 29Si hyperfine interactions. The chemical accessibility of the reduced sites is probed using ammonia as probe molecule. Evidence is found for the coordination of a single ammonia molecule. Comparison to similar systems, such as TiAlPO‐5, reveals clear differences in the coordination chemistry of the reduced Ti sites in the two solids, which may be understood considering the different electronic properties of the solid frameworks. 相似文献
72.
Andreas Marc Palmer Vittoria Chiesa Hans Christof Holst Jacques Le Paih Antonio Zanotti-Gerosa Ulrike Nettekoven 《Tetrahedron: Asymmetry》2008,19(17):2102-2110
The asymmetric hydrogenation of complex heterocyclic ketones 1 in the presence of the novel catalyst RuCl2[(S)-Xyl-P-Phos][(S)-DAIPEN] and a base afforded the corresponding alcohols 2 in good enantiomeric purity. The outcome of the reaction depended on the substitution pattern of the ketone and the stoichiometry of the base. After optimization of the reaction conditions, the pure alcohols 2a and 2b were isolated in good yield (>70%) and enantiomeric purity (>93% ee) and used as key intermediates for the synthesis of the pharmaceutically active 3,6,7,8-tetrahydrochromeno[7,8-d]imidazoles 3a and 3b. 相似文献
73.
Selena J. Lockyer Alessandro Chiesa Grigore A. Timco Eric J. L. McInnes Tom S. Bennett Inigo J. Vitorica-Yrezebal Stefano Carretta Richard E. P. Winpenny 《Chemical science》2021,12(26):9104
The implementation of a quantum computer requires both to protect information from environmental noise and to implement quantum operations efficiently. Achieving this by a fully fault-tolerant platform, in which quantum gates are implemented within quantum-error corrected units, poses stringent requirements on the coherence and control of such hardware. A more feasible architecture could consist of connected memories, that support error-correction by enhancing coherence, and processing units, that ensure fast manipulations. We present here a supramolecular {Cr7Ni}–Cu system which could form the elementary unit of this platform, where the electronic spin 1/2 of {Cr7Ni} provides the processor and the naturally isolated nuclear spin 3/2 of the Cu ion is used to encode a logical unit with embedded quantum error-correction. We demonstrate by realistic simulations that microwave pulses allow us to rapidly implement gates on the processor and to swap information between the processor and the quantum memory. By combining the storage into the Cu nuclear spin with quantum error correction, information can be protected for times much longer than the processor coherence.The implementation of a quantum computer requires protecting of information from noise and the ability to perform quantum gates. We present a molecular architecture providing both these ingredients, via an electronic spin 1/2 processor and a nuclear spin 3/2 memory. 相似文献
74.
Maurelli S Vishnuvarthan M Berlier G Chiesa M 《Physical chemistry chemical physics : PCCP》2012,14(2):987-995
Continuous Wave (CW), pulse Electron Paramagnetic Resonance (EPR) and pulse Electron Nuclear Double Resonance (ENDOR) spectroscopies, in conjunction with UV-Vis and Infrared (IR) spectroscopies, are used to investigate the chemical reactivity of tetrahedrally coordinated Ti(3+) ions isomorphously substituted in the framework of AlPO-5 towards NH(3) and O(2). The coordination of ammonia to Ti(3+) centres is followed in detail by complementary vibrational and electron magnetic resonance techniques. In particular HYSCORE spectra allow identifying the coordination of two ammonia molecules to Ti(3+) centres resolving the full hyperfine and quadrupole (14)N coupling tensors. The reactivity of the reduced TiAlPO sample towards molecular oxygen is detailed by means of CW-EPR and pulse ENDOR spectroscopy. (17)O(2) is employed, allowing to establish the formation of a "side-on" η(2) O(2)(-)-Ti(4+) electrostatic complex. Pulse ENDOR spectra provide detailed information on the local environment of the formed superoxide radical anion which acts as a paramagnetic probe, providing evidence for Ti-O-Ti oligomeric species. 相似文献
75.
S Maurelli M Chiesa E Giamello RM Leithall R Raja 《Chemical communications (Cambridge, England)》2012,48(69):8700-8702
Vanadium and titanium bimetallic AlPO-5 molecular sieves have been synthesized and characterized by means of Electron Spin Echo detected EPR and Hyperfine Sublevel Correlation (HYSCORE) spectroscopy. Direct evidence for framework substitution of redox-active Ti ions and VO(2+) units at Al sites is provided through the detection of large (31)P hyperfine couplings. 相似文献
76.
Davide Ranieri Dr. Alberto Privitera Dr. Fabio Santanni Dr. Karolina Urbanska Dr. Grant J. Strachan Dr. Brendan Twamley Prof. Dr. Enrico Salvadori Dr. Yu-Kai Liao Prof. Dr. Mario Chiesa Prof. Dr. Mathias O. Senge Prof. Dr. Federico Totti Prof. Dr. Lorenzo Sorace Prof. Dr. Roberta Sessoli 《Angewandte Chemie (International ed. in English)》2023,62(48):e202312936
In the development of two-qubit quantum gates, precise control over the intramolecular spin-spin interaction between molecular spin units plays a pivotal role. A weak but measurable exchange coupling is especially important for achieving selective spin addressability that allows controlled manipulation of the computational basis states |00⟩ |01⟩ |10⟩ |11⟩ by microwave pulses. Here, we report the synthesis and Electron Paramagnetic Resonance (EPR) study of a heterometallic meso-meso (m-m) singly-linked VIVO−CuII porphyrin dimer. X-band continuous wave EPR measurements in frozen solutions suggest a ferromagnetic exchange coupling of ca. 8 ⋅ 10−3 cm−1. This estimation is supported by Density Functional Theory calculations, which also allow disentangling the ferro- and antiferromagnetic contributions to the exchange. Pulsed EPR experiments show that the dimer maintains relaxation times similar to the monometallic CuII porphyrins. The addressability of the two individual spins is made possible by the different g -tensors of VIV and CuII-ions, in contrast to homometallic dimers where tilting of the porphyrin planes plays a key role. Therefore, single-spin addressability in the heterometallic dimer can be maintained even with small tilting angles, as expected when deposited on surface, unlocking the full potential of molecular quantum gates for practical applications. 相似文献
77.
Gianfranco Pacchioni Sabrina Sicolo Cristiana Di Valentin Mario Chiesa Elio Giamello 《ChemInform》2008,39(44):no-no
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献
78.
Dr. Fabian Hecker Lisa Fries Dr. Markus Hiller Prof. Dr. Mario Chiesa Prof. Dr. Marina Bennati 《Angewandte Chemie (International ed. in English)》2023,62(4):e202213700
The hydration structure of nitroxide radicals in aqueous solutions is elucidated by advanced 17O hyperfine (hf) spectroscopy with support of quantum chemical calculations and MD simulations. A piperidine and a pyrrolidine-based nitroxide radical are compared and show clear differences in the preferred directionality of H-bond formation. We demonstrate that these scenarios are best represented in 17O hf spectra, where in-plane coordination over -type H-bonding leads to little spin density transfer on the water oxygen and small hf couplings, whereas -type perpendicular coordination generates much larger hf couplings. Quantitative analysis of the spectra based on MD simulations and DFT predicted hf parameters is consistent with a distribution of close solvating water molecules, in which directionality is influenced by subtle steric effects of the ring and the methyl group substituents. 相似文献
79.
Dr. Fabio Pirro Dr. Salvatore La Gatta Dr. Federica Arrigoni Dr. Antonino Famulari Dr. Ornella Maglio Prof. Pompea Del Vecchio Prof. Mario Chiesa Prof. Luca De Gioia Prof. Luca Bertini Dr. Marco Chino Prof. Flavia Nastri Prof. Angela Lombardi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202211552
De novo metalloprotein design is a remarkable approach to shape protein scaffolds toward specific functions. Here, we report the design and characterization of Due Rame 1 (DR1), a de novo designed protein housing a di-copper site and mimicking the Type 3 (T3) copper-containing polyphenol oxidases (PPOs). To achieve this goal, we hierarchically designed the first and the second di-metal coordination spheres to engineer the di-copper site into a simple four-helix bundle scaffold. Spectroscopic, thermodynamic, and functional characterization revealed that DR1 recapitulates the T3 copper site, supporting different copper redox states, and being active in the O2-dependent oxidation of catechols to o-quinones. Careful design of the residues lining the substrate access site endows DR1 with substrate recognition, as revealed by Hammet analysis and computational studies on substituted catechols. This study represents a premier example in the construction of a functional T3 copper site into a designed four-helix bundle protein. 相似文献