Single-molecule magnets display magnetic bistability of molecular origin, which may one day be exploited in magnetic data storage devices. Recently it was realised that increasing the magnetic moment of polynuclear molecules does not automatically lead to a substantial increase in magnetic bistability. Attention has thus increasingly focussed on ions with large magnetic anisotropies, especially lanthanides. In spite of large effective energy barriers towards relaxation of the magnetic moment, this has so far not led to a big increase in magnetic bistability. Here we present a comprehensive study of a mononuclear, tetrahedrally coordinated cobalt(II) single-molecule magnet, which has a very high effective energy barrier and displays pronounced magnetic bistability. The combined experimental-theoretical approach enables an in-depth understanding of the origin of these favourable properties, which are shown to arise from a strong ligand field in combination with axial distortion. Our findings allow formulation of clear design principles for improved materials.
A 5-pulse version of the Double Electron Electron Resonance (DEER) experiment with Carr-Purcell delays and an additional pump pulse has been shown to significantly extend the experimentally accessible distance range in cases where nuclear spin diffusion dominates electron spin phase memory loss [Borbat et al., J. Phys. Chem. Lett., 2013, 4, 170]. We show that the sequence also prolongs coherence decay for spin labels in or near lipid bilayers, where this decay is mono-exponential. Compared to 4-pulse DEER, 5-pulse DEER suffers from additional artefacts that stem from pulse imperfection and excitation band overlap. Only some of these artefacts can be suppressed by phase cycling and the remaining ones have hindered widespread utilization of the method. Here, we report previously unknown additional artefact contributions stemming from overlap between the excitation bands of the microwave pulses that introduce additional dipolar evolution pathways. Experimental conditions are analyzed in detail that suppress these as well as the already known artefacts. Such suppression results in data that contain at most the partial excitation artefact, which can be deliberately shifted in time by a change in pulse timing without affecting the wanted contribution.
Proteins
composed of multiple domains allow for structural heterogeneity
and interdomain dynamics that may be vital for function. Intradomain
structures and dynamics can influence interdomain conformations and vice versa. However, no established structure determination
method is currently available that can probe the coupling of these
motions. The protein Pin1 contains separate regulatory and catalytic
domains that sample “extended” and “compact”
states, and ligand binding changes this equilibrium. Ligand binding
and interdomain distance have been shown to impact the activity of
Pin1, suggesting interdomain allostery. In order to characterize the
conformational equilibrium of Pin1, we describe a novel method to
model the coupling between intra- and interdomain dynamics at atomic
resolution using multistate ensembles. The method uses time-averaged
nuclear magnetic resonance (NMR) restraints and double electron–electron
resonance (DEER) data that resolve distance distributions. While the
intradomain calculation is primarily driven by exact nuclear Overhauser
enhancements (eNOEs), J couplings, and residual dipolar
couplings (RDCs), the relative domain distribution is driven by paramagnetic
relaxation enhancement (PREs), RDCs, interdomain NOEs, and DEER. Our
data support a 70:30 population of the compact and extended states
in apo Pin1. A multistate ensemble describes these conformations simultaneously,
with distinct conformational differences located in the interdomain
interface stabilizing the compact or extended states. We also describe
correlated conformations between the catalytic site and interdomain
interface that may explain allostery driven by interdomain contact.
We show that oligo(phenyleneethynylene)s (oligoPEs) are ideal spacers for calibrating dye pairs used for Förster resonance energy transfer (FRET). Ensemble FRET measurements on linear and kinked diads with such spacers show the expected distance-and orientation-dependence of FRET. Measured FRET efficiencies match excellently with those predicted using a harmonic segmented chain model, which was validated by end-to-end distance distributions obtained from pulsed electron paramagnetic resonance measurements on spin-labeled oligoPEs with comparable label distances. Förster resonance energy transfer (FRET) 1,2 experiments exploit the distance-dependence of dipolar coupling between an electronically excited fluorescent dye, acting as energy donor, and a chromophore in its ground state, acting as energy acceptor. Since FRET provides a means for sensing inter-and intramolecular distances in the range of 30-100 Å, many FRET-based techniques have emerged, 3-9 e.g., in studies of protein folding and protein interaction. 10-13 Förster's theory 1 relates the FRET efficiency E with the inter-dye distance rda according to:
Determining distributed exchange couplings is important for understanding the properties of synthetic magnetic molecules. Such distributions can be determined from pulsed dipolar spectroscopy (PDS) data, but this is challenging due...
Quinonoid bridges are well-suited for generating dinuclear assemblies that might display various bistable properties. In this contribution we present two diiron(II) complexes where the iron(II) centers are either bridged by the doubly deprotonated form of a symmetrically substituted quinonoid bridge, 2,5-bis[4-(isopropyl)anilino]-1,4-benzoquinone (HL2') with a [O,N,O,N] donor set, or with the doubly deprotonated form of an unsymmetrically substituted quinonoid bridge, 2-[4-(isopropyl)anilino]-5-hydroxy-1,4-benzoquinone (HL5') with a [O,O,O,N] donor set. Both complexes display temperature-induced spin crossover (SCO). The nature of the SCO is strongly dependent on the bridging ligand, with only the complex with the [O,O,O,N] donor set displaying a prominent hysteresis loop of about 55 K. Importantly, only the latter complex also shows a pronounced light-induced spin state change. Furthermore, both complexes can be oxidized to the mixed-valent iron(II)-iron(III) form, and the nature of the bridge determines the Robin and Day classification of these forms. Both complexes have been probed by a battery of electrochemical, spectroscopic, and magnetic methods, and this combined approach is used to shed light on the electronic structures of the complexes and on bistability. The results presented here thus show the potential of using the relatively new class of unsymmetrically substituted bridging quinonoid ligands for generating intriguing bistable properties and for performing site-specific magnetic switching.
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