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- W2309426812 abstract "Abstract High‐spin gadolinium(III) and manganese(II) complexes have emerged as alternatives to standard nitroxide radical spin labels for measuring nanometric distances by using pulsed electron–electron double resonance (PELDOR or DEER) at high fields/frequencies. For certain complexes, particularly those with relatively small zero‐field splitting (ZFS) and short distances between the two metal centers, the pseudosecular term of the dipolar coupling Hamiltonian is non‐negligible. However, in general, the contribution from this term during conventional data analysis is masked by the flexibility of the molecule of interest and/or the long tethers connecting them to the spin labels. The efficient synthesis of a model system consisting of two [Mn(dota)] 2− (MnDOTA; DOTA 4− =1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetate) directly connected to the ends of a central rodlike oligo(phenylene–ethynylene) (OPE) spacer is reported. The rigidity of the OPE is confirmed by Q‐band PELDOR measurements on a bis‐nitroxide analogue. The Mn II −Mn II distance distribution profile determined by W‐band PELDOR is in reasonable agreement with one simulated by using a simple rotamer analysis. The small degree of flexibility arising from the linking MnDOTA arm appears to outweigh the contribution from the pseudosecular term at this interspin distance. This study illustrates the potential of MnDOTA‐based spin labels for measuring fairly short nanometer distances, and also presents an interesting candidate for in‐depth studies of pulsed dipolar spectroscopy methods on Mn II −Mn II systems." @default.
- W2309426812 created "2016-06-24" @default.
- W2309426812 creator A5028294643 @default.
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- W2309426812 creator A5069121068 @default.
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- W2309426812 creator A5075694197 @default.
- W2309426812 date "2016-04-18" @default.
- W2309426812 modified "2023-10-14" @default.
- W2309426812 title "A Bis-Manganese(II)-DOTA Complex for Pulsed Dipolar Spectroscopy" @default.
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