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Achieving control of phase memory relaxation times ( T m ) 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 T m in metal ions. We synthesized and studied a series of five V( iv ) complexes with brominated catecholate ligands, [V(C 6 H 4−n Br n O 2 ) 3 ] 2− ( n = 0, 1, 2, and 4), where the 79/81 Br and 1 H 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 T m for the V( iv ) ion. Notably, we show that it is possible for two molecules to have starkly different (by 50%) T m 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 T m for the bound metal ion.
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Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring
Cyanuric triazide reacts with several transition metal precursors, extruding one equivalent of N 2 and reducing the putative diazidotriazeneylnitrene species by two electrons, which rearranges to N -(1′ H -[1,5′-bitetrazol]-5-yl)methanediiminate (biTzI 2− ) dianionic ligand, which ligates the metal and dimerizes, and is isolated from pyridine as [M(biTzI)] 2 Py 6 (M = Mn, Fe, Zn, Cu, Ni). Reagent scope, product analysis, and quantum chemical calculations were combined to elucidate the mechanism of formation as a two-electron reduction preceding ligand rearrangement.
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- Award ID(s):
- 1800105
- PAR ID:
- 10292311
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 12
- Issue:
- 6
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 2268 to 2275
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d0sc04949b
