Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes

Cassidy E. Jackson, Chun Yi Lin, Spencer H. Johnson, Johan Van Tol, Joseph M. Zadrozny

Research output: Contribution to journalArticle

Abstract

Achieving control of phase memory relaxation times (Tm) in metal ions is an important goal of molecular spintronics. Herein we provide the first evidence that nuclear-spin patterning in the ligand shell is an important handle to modulate Tm in metal ions. We synthesized and studied a series of five V(iv) complexes with brominated catecholate ligands, [V(C6H4-nBrnO2)3]2- (n = 0, 1, 2, and 4), where the 79/81Br and 1H nuclear spins are arranged in different substitutional patterns. High-field, high-frequency (120 GHz) pulsed electron paramagnetic resonance spectroscopic analysis of this series reveals a pattern-dependent variation in Tm for the V(iv) ion. Notably, we show that it is possible for two molecules to have starkly different (by 50%) Tm values despite the same chemical composition. Nuclear magnetic resonance analyses of the protons on the ligand shell suggest that relative chemical shift (δ), controlled by the patterning of nuclear spins, is an important underlying design principle. Here, having multiple ligand-based protons with nearly identical chemical shift values in the ligand shell will, ultimately, engender a short Tm for the bound metal ion.

Original languageEnglish
Pages (from-to)8447-8454
Number of pages8
JournalChemical Science
Volume10
Issue number36
DOIs
Publication statusPublished - 2019 Jan 1

Fingerprint

Spin dynamics
Ligands
Electrons
Metal ions
Chemical shift
Protons
Magnetoelectronics
Spectroscopic analysis
Relaxation time
Paramagnetic resonance
Nuclear magnetic resonance
Ions
Data storage equipment
Molecules
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Jackson, Cassidy E. ; Lin, Chun Yi ; Johnson, Spencer H. ; Van Tol, Johan ; Zadrozny, Joseph M. / Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes. In: Chemical Science. 2019 ; Vol. 10, No. 36. pp. 8447-8454.
@article{11c140049b3c4239a248e73ca4cb9b13,
title = "Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes",
abstract = "Achieving control of phase memory relaxation times (Tm) in metal ions is an important goal of molecular spintronics. Herein we provide the first evidence that nuclear-spin patterning in the ligand shell is an important handle to modulate Tm in metal ions. We synthesized and studied a series of five V(iv) complexes with brominated catecholate ligands, [V(C6H4-nBrnO2)3]2- (n = 0, 1, 2, and 4), where the 79/81Br and 1H nuclear spins are arranged in different substitutional patterns. High-field, high-frequency (120 GHz) pulsed electron paramagnetic resonance spectroscopic analysis of this series reveals a pattern-dependent variation in Tm for the V(iv) ion. Notably, we show that it is possible for two molecules to have starkly different (by 50{\%}) Tm values despite the same chemical composition. Nuclear magnetic resonance analyses of the protons on the ligand shell suggest that relative chemical shift (δ), controlled by the patterning of nuclear spins, is an important underlying design principle. Here, having multiple ligand-based protons with nearly identical chemical shift values in the ligand shell will, ultimately, engender a short Tm for the bound metal ion.",
author = "Jackson, {Cassidy E.} and Lin, {Chun Yi} and Johnson, {Spencer H.} and {Van Tol}, Johan and Zadrozny, {Joseph M.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1039/c9sc02899d",
language = "English",
volume = "10",
pages = "8447--8454",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "36",

}

Jackson, CE, Lin, CY, Johnson, SH, Van Tol, J & Zadrozny, JM 2019, 'Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes', Chemical Science, vol. 10, no. 36, pp. 8447-8454. https://doi.org/10.1039/c9sc02899d

Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes. / Jackson, Cassidy E.; Lin, Chun Yi; Johnson, Spencer H.; Van Tol, Johan; Zadrozny, Joseph M.

In: Chemical Science, Vol. 10, No. 36, 01.01.2019, p. 8447-8454.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes

AU - Jackson, Cassidy E.

AU - Lin, Chun Yi

AU - Johnson, Spencer H.

AU - Van Tol, Johan

AU - Zadrozny, Joseph M.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Achieving control of phase memory relaxation times (Tm) in metal ions is an important goal of molecular spintronics. Herein we provide the first evidence that nuclear-spin patterning in the ligand shell is an important handle to modulate Tm in metal ions. We synthesized and studied a series of five V(iv) complexes with brominated catecholate ligands, [V(C6H4-nBrnO2)3]2- (n = 0, 1, 2, and 4), where the 79/81Br and 1H nuclear spins are arranged in different substitutional patterns. High-field, high-frequency (120 GHz) pulsed electron paramagnetic resonance spectroscopic analysis of this series reveals a pattern-dependent variation in Tm for the V(iv) ion. Notably, we show that it is possible for two molecules to have starkly different (by 50%) Tm values despite the same chemical composition. Nuclear magnetic resonance analyses of the protons on the ligand shell suggest that relative chemical shift (δ), controlled by the patterning of nuclear spins, is an important underlying design principle. Here, having multiple ligand-based protons with nearly identical chemical shift values in the ligand shell will, ultimately, engender a short Tm for the bound metal ion.

AB - Achieving control of phase memory relaxation times (Tm) in metal ions is an important goal of molecular spintronics. Herein we provide the first evidence that nuclear-spin patterning in the ligand shell is an important handle to modulate Tm in metal ions. We synthesized and studied a series of five V(iv) complexes with brominated catecholate ligands, [V(C6H4-nBrnO2)3]2- (n = 0, 1, 2, and 4), where the 79/81Br and 1H nuclear spins are arranged in different substitutional patterns. High-field, high-frequency (120 GHz) pulsed electron paramagnetic resonance spectroscopic analysis of this series reveals a pattern-dependent variation in Tm for the V(iv) ion. Notably, we show that it is possible for two molecules to have starkly different (by 50%) Tm values despite the same chemical composition. Nuclear magnetic resonance analyses of the protons on the ligand shell suggest that relative chemical shift (δ), controlled by the patterning of nuclear spins, is an important underlying design principle. Here, having multiple ligand-based protons with nearly identical chemical shift values in the ligand shell will, ultimately, engender a short Tm for the bound metal ion.

UR - http://www.scopus.com/inward/record.url?scp=85072596540&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85072596540&partnerID=8YFLogxK

U2 - 10.1039/c9sc02899d

DO - 10.1039/c9sc02899d

M3 - Article

AN - SCOPUS:85072596540

VL - 10

SP - 8447

EP - 8454

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 36

ER -