Journal article
Singly and triply linked magnetic porphyrin lanthanide arrays
- Abstract:
- The introduction of paramagnetic metal centers into a conjugated π-system is a promising approach toward engineering spintronic materials. Here, we report an investigation of two types of spin-bearing dysprosium(III) and gadolinium(III) porphyrin dimers: singly meso–meso-linked dimers with twisted conformations and planar edge-fused β,meso,β-linked tapes. The rare-earth spin centers sit out of the plane of the porphyrin, so that the singly linked dimers are chiral, and their enantiomers can be resolved, whereas the edge-fused tape complexes can be separated into syn and anti stereoisomers. We compare the crystal structures, UV–vis–NIR absorption spectra, electrochemistry, EPR spectroscopy, and magnetic behavior of these complexes. Low-temperature SQUID magnetometry measurements reveal intramolecular antiferromagnetic exchange coupling between the GdIII centers in the edge-fused dimers (syn isomer: J = −51 ± 2 MHz; anti isomer: J = −19 ± 3 MHz), whereas no exchange coupling is detected in the singly linked twisted complex. The phase-memory times, Tm, are in the range of 8–10 μs at 3 K, which is long enough to test quantum computational schemes using microwave pulses. Both the syn and anti Dy2 edge-fused tapes exhibit single-molecule magnetic hysteresis cycles at temperatures below 0.5 K with slow magnetization dynamics.
- Publication status:
- Published
- Peer review status:
- Peer reviewed
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(Preview, Version of record, pdf, 6.5MB, Terms of use)
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(Preview, Supplementary materials, pdf, 10.8MB, Terms of use)
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- Publisher copy:
- 10.1021/jacs.2c02084
Authors
- Publisher:
- American Chemical Society
- Journal:
- Journal of the American Chemical Society More from this journal
- Volume:
- 144
- Issue:
- 19
- Pages:
- 8693–8706
- Publication date:
- 2022-05-03
- Acceptance date:
- 2022-04-20
- DOI:
- EISSN:
-
1520-5126
- ISSN:
-
0002-7863
- Language:
-
English
- Keywords:
- Pubs id:
-
1256217
- Local pid:
-
pubs:1256217
- Deposit date:
-
2022-05-04
- ARK identifier:
Terms of use
- Copyright holder:
- Van Raden et al.
- Copyright date:
- 2022
- Rights statement:
- © 2022 The Authors. Published by American Chemical Society. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.
- Licence:
- CC Attribution (CC BY)
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