4
views
0
recommends
+1 Recommend
0 collections
    0
    shares
      • Record: found
      • Abstract: found
      • Article: found
      Is Open Access

      Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

      review-article
      Chemical Reviews
      American Chemical Society

      Read this article at

      Bookmark
          There is no author summary for this article yet. Authors can add summaries to their articles on ScienceOpen to make them more accessible to a non-specialist audience.

          Abstract

          The number of rare earth (RE) starting materials used in synthesis is staggering, ranging from simple binary metal-halide salts to borohydrides and “designer reagents” such as alkyl and organoaluminate complexes. This review collates the most important starting materials used in RE synthetic chemistry, including essential information on their preparations and uses in modern synthetic methodologies. The review is divided by starting material category and supporting ligands ( i.e., metals as synthetic precursors, halides, borohydrides, nitrogen donors, oxygen donors, triflates, and organometallic reagents), and in each section relevant synthetic methodologies and applications are discussed.

          Related collections

          Most cited references705

          • Record: found
          • Abstract: not found
          • Article: not found

          Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides

            Bookmark
            • Record: found
            • Abstract: found
            • Article: not found

            Molecular magnetic hysteresis at 60 kelvin in dysprosocenium

            Lanthanides have been investigated extensively for potential applications in quantum information processing and high-density data storage at the molecular and atomic scale. Experimental achievements include reading and manipulating single nuclear spins, exploiting atomic clock transitions for robust qubits and, most recently, magnetic data storage in single atoms. Single-molecule magnets exhibit magnetic hysteresis of molecular origin—a magnetic memory effect and a prerequisite of data storage—and so far lanthanide examples have exhibited this phenomenon at the highest temperatures. However, in the nearly 25 years since the discovery of single-molecule magnets, hysteresis temperatures have increased from 4 kelvin to only about 14 kelvin using a consistent magnetic field sweep rate of about 20 oersted per second, although higher temperatures have been achieved by using very fast sweep rates (for example, 30 kelvin with 200 oersted per second). Here we report a hexa-tert-butyldysprosocenium complex—[Dy(Cpttt)2][B(C6F5)4], with Cpttt = {C5H2tBu3-1,2,4} and tBu = C(CH3)3—which exhibits magnetic hysteresis at temperatures of up to 60 kelvin at a sweep rate of 22 oersted per second. We observe a clear change in the relaxation dynamics at this temperature, which persists in magnetically diluted samples, suggesting that the origin of the hysteresis is the localized metal–ligand vibrational modes that are unique to dysprosocenium. Ab initio calculations of spin dynamics demonstrate that magnetic relaxation at high temperatures is due to local molecular vibrations. These results indicate that, with judicious molecular design, magnetic data storage in single molecules at temperatures above liquid nitrogen should be possible.
              Bookmark
              • Record: found
              • Abstract: found
              • Article: not found

              Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet

              Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation [(CpiPr5)Dy(Cp*)]+ (CpiPr5 = penta-iso-propylcyclopentadienyl, Cp* = pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of Ueff = 1,541 cm–1 is also measured. The magnetic blocking temperature of TB = 80 K for this cation overcomes an essential barrier towards the development of nanomagnet devices that function at practical temperatures.
                Bookmark

                Author and article information

                Journal
                Chem Rev
                Chem Rev
                cr
                chreay
                Chemical Reviews
                American Chemical Society
                0009-2665
                1520-6890
                31 January 2022
                23 March 2022
                : 122
                : 6
                : 6040-6116
                Affiliations
                [1]School of Chemistry, University of Leicester , LE1 7RH Leicester, U.K.
                Author notes
                Author information
                https://orcid.org/0000-0002-1743-8338
                Article
                10.1021/acs.chemrev.1c00842
                9007467
                35099940
                8a9c03cf-af45-461c-b247-963a8cd07791
                © 2022 American Chemical Society

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 30 September 2021
                Funding
                Funded by: Engineering and Physical Sciences Research Council, doi 10.13039/501100000266;
                Award ID: EP/W00691X/1
                Funded by: School of Chemistry, University of Leicester, doi NA;
                Award ID: NA
                Categories
                Review
                Custom metadata
                cr1c00842
                cr1c00842

                Chemistry
                Chemistry

                Comments

                Comment on this article