Unusual metal centres/coordination spheres in spin crossover compounds
COORDINATION CHEMISTRY REVIEWS
Authors: Olguin, Juan
Abstract
The most widely studied spin crossover (SCO) systems are those involving hexacoordinate iron(II) complexes immerse in the "magic" N-6 coordination sphere. In this review the properties of SCO-active metal complexes containing unusual metal centres and/or coordination spheres are analysed, except for Fe3+ complexes that have been recently reviewed. The SCO-properties of the less studied SCO metal centres Cr2+, Mn2+, Mn3+ and Co2+ are presented, showing great advances in the development of bistable materials containing first row transition metals other than Fe. Finally, an analysis of the changes in the structural parameters, bond lengths and angles, during the spin conversion is presented for those complexes structurally characterised by X-ray crystallography in both high- and low-spin states. (C) 2019 Elsevier B.V. All rights reserved.
Randomized trial of polychromatic blue-enriched light for circadian phase shifting, melatonin suppression, and alerting responses
PHYSIOLOGY & BEHAVIOR
Authors: Hanifin, J. P.; Lockley, S. W.; Cecil, K.; West, K.; Jablonski, M.; Warfield, B.; James, M.; Ayers, M.; Byrne, B.; Gerner, E.; Pineda, C.; Rollag, M.; Brainard, G. C.
Abstract
Wavelength comparisons have indicated that circadian phase-shifting and enhancement of subjective and EEG correlates of alertness have a higher sensitivity to short wavelength visible light. The aim of the current study was to test whether polychromatic light enriched in the blue portion of the spectrum (17,000 K) has increased efficacy for melatonin suppression, circadian phase-shifting, and alertness as compared to an equal photon density exposure to a standard white polychromatic light (4000 K). Twenty healthy participants were studied in a time-free environment for 7 days. The protocol included two baseline days followed by a 26-h constant routine (CR1) to assess initial circadian phase. Following CR1, participants were exposed to a full-field fluorescent light (1 x 10(14) photons/cm(2)/s, 4000 K or 17,000 K, n = 10/condition) for 6.5 h during the biological night. Following an 8 h recovery sleep, a second 30-h CR was performed. Melatonin suppression was assessed from the difference during the light exposure and the corresponding clock time 24 h earlier during CR1. Phase-shifts were calculated from the clock time difference in dim light melatonin onset time (DLMO) between CR1 and CR2. Blue-enriched light caused significantly greater suppression of melatonin than standard light ((mean +/- SD) 70.9 +/- 19.6% and 42.8 +/- 29.1%, respectively, p < 0.05). There was no significant difference in the magnitude of phase delay shifts. Blue-enriched light significantly improved subjective alertness (p < 0.05) but no differences were found for objective alertness. These data contribute to the optimization of the short wavelength enriched spectra and intensities needed for circadian, neuroendocrine and neurobehavioral regulation.