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Spin-Vertical Cavity Surface Emitting Lasers (spin-VCSELs) are undergoing increasing research effort for new paradigms in high-speed optical communications and photon-enabled computing. To date research in spin-VCSELs has mostly focused on Quantum-Well (QW) devices. However, novel Quantum-Dot (QD) spin-VCSELs, offer enhanced parameter controls permitting the effective, dynamical and ultrafast manipulation of their light emissions polarization. In the present contribution we investigate in detail the operation of QD spin-VCSELs subject to polarization modulation for their use as ultrafast light sources in optical communication systems. We reveal that QD spin-VCSELs outperform their QW counterparts in terms of modulation efficiency, yielding a nearly two-fold improvement. We also analyse the impact of key device parameters in QD spin-VCSELs (e.g. photon decay rate and intra-dot relaxation rate) on the large signal modulation performance with regard to optical modulation amplitude and eye-diagram opening penalty. We show that in addition to exhibiting enhanced polarization modulation performance for data rates up to 250Gbps, QD spin-VCSELs enable operation in dual (ground and excited state) emission thus allowing future exciting routes for multiplexing of information in optical communication links.

The unusual ferromagnetically coupled compound was prepared by the use of Me3SiN3 with the metal ions being exclusively bridged by end-on N3–. Th cationic molecule is a rare example of a 3d-metal cluster exhibiting a “Janus”-faced SMM behavior for the dried and wet forms., A rare disk-like single-molecule magnet (SMM) exclusively bridged by end-on azides with a spin ground state of S = 14 was prepared by the reaction of a divalent FeII precursor with Me3SiN3 under basic conditions. AC magnetic susceptibility studies revealed unusual, “Janus”-faced SMM behavior for the dried and pristine forms of the compound attributed to solvation/de-solvation effects of the coordinated MeCN ligands which leads to alterations in the crystal field and symmetry of the metal ions. DFT calculations confirmed the ferromagnetic nature of the interactions between the FeII spin carriers with the zero-field splitting parameters D = –0.2323 cm–1 and E/D = 0.027. The results have important implications for the future study of single-molecule magnets incorporating volatile solvent molecules in the first coordination sphere of the metal ions and their effect on the relaxation dynamics.

ID: 1135 In: Polyhedron, 131-142. Summary: Graphical abstractThe combination of cyanate, carboxylate and 2-(hydroxymethyl)pyridine ligands in higher oxidation state Mn cluster chemistry has led to two different families of MnII/III16and MnII/III18clusters with interesting topologies and nanoscale dimensions.AbstractThe employment of cyanato (OCN−) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)) and [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O2CMe)2·4H2O, hmpH, NaOCN and NEt3in solvent MeOH or EtOH afford the isostructural complexes [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)). The [Mn16(μ4-O)4(μ3-O)4(μ-OMe)4(μ3-OR)6(μ-OR)6]10+core of representative complex1comprises a MnII4MnIII4double-cubane subunit attached on either side to two symmetry-related MnIIMnIII3defective dicubanes. A similar reaction of Mn(O2CR)2·4H2O, hmpH, NaOCN and NEt3, but in solvent MeCN, led instead to the formation of [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). Compounds3and4are very similar to each other and can be described as a central [MnIII4(μ-O)6] rodlike subunit attached on either side to two symmetry-related [Mn7O9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possibleS = 2 or 1 (for1and2) andS = 0 (for3and4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear MnII/IIIcomplexes with structures different than these obtained from the use of the related azides.

The initial employment of cyanato groups in higher oxidation state manganese cluster chemistry, in conjunction with the gem-diolate form of di-2-pyridylketone or 2,6-diacetylpyridine dioxime chelate ligands, has afforded structurally interesting MnII/III14 and Mn II/III/IV16 clusters, respectively. In both complexes, the end-on bridging cyanato groups show an obvious preference in binding through their O atom, a significantly different ligation than that for the homoatomic-type N3- ligand. The Mn14 compound shows entirely visible out-of-phase signals below 5 K and large hysteresis loops below 2 K. The use of cyanato groups in higher oxidation state Mn cluster chemistry, in combination with the gem-diolate form of di-2-pyridylketone or 2,6-diacetylpyridine dioxime chelate ligands, has afforded structurally new Mn14 and Mn16 clusters, respectively the Mn14 compound shows entirely visible out-of-phase signals below 5 K and large hysteresis loops below 2 K. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 13 2286 2290 Cited By :12

A Mn III 4Ni II 4 molecular square exhibiting slow magnetization relaxation has been prepared from the reaction of a Mn II 4Mn III 6Mn IV 2 cluster and a simple Ni II source. © The Royal Society of Chemistry 2012. 41 16 4744 4747 Cited By :8

Η σύνθεση και ο χαρακτηρισμός πλειάδων των μετάλλων μετάπτωσης σε ενδιάμεσες οξειδωτικές βαθμίδες αποτελεί σήμερα έναν από τους κύριους ερευνητικούς στόχους πολλών επιστημονικών ομάδων παγκοσμίως εξαιτίας των εφαρμογών που βρίσκουν σε διάφορα επιστημονικά πεδία, όπως στη βιοανόργανη χημεία, στην επιστήμη των υλικών, στη μοριακή φυσική και ηλεκτρονική, και στη θεωρητική χημεία. Οι πλειάδες αυτές περιέχουν πολλές φορές έναν ασυνήθιστα μεγάλο αριθμό ασυζεύκτων ηλεκτρονίων στη θεμελιώδη κατάσταση και παρουσιάζουν εξαιρετικό ενδιαφέρον από μαγνητικής απόψεως. Αυτό συμβαίνει γιατί μια υψηλή τιμή spin στη θεμελιώδη κατάσταση είναι αναγκαία (άλλα όχι ικανή) συνθήκη ώστε αυτού του είδους οι σύμπλοκες ενώσεις να εμφανίζουν το φαινόμενο του μονομοριακού μαγνητισμού (single-molecule magnetism). Στην παρούσα Εργασία μελετήθηκε το σύστημα αντίδρασης μαγγάνιο/2-πυριδυλομεθανόλη (hmpH), παρουσία ή απουσία κυανικών ιόντων (OCN-) και κάτω από βασικές συνθήκες, το οποίο οδήγησε στην απομόνωση και το δομικό (μέσω κρυσταλλογραφίας ακτίνων-Χ σε μονοκρυστάλλους) και μαγνητοχημικό χαρακτηρισμό των πλειάδων [Mn7(OH)3(OCN)3(hmp)9](ClO4)2 (1), [Mn16O8(OMe)4(OCN)4(O2CMe)12(hmp)6(MeOH)2] (2), [Mn18O14(O2CMe)18(hmp)4(hmpH)2(H2O)2] (3) και [Mn18O14(O2CEt)18(hmp)4(hmpH)2(H2O)2] (4). Οι πλειάδες 1-4 είναι μικτού-σθένους (ΙΙ/ΙΙΙ). Το σύμπλοκο 1 αποτελεί ένα νέο μέλος μιας μεγάλης οικογένειας επταπυρηνικών συμπλόκων με το δομικό πυρήνα τους να περιλαμβάνει έξι ιόντα Mn διευθετημένα κυκλικά γύρω από ένα έβδομο κεντρικό ιόν Mn2+. Τα σύμπλοκα 2, 3 και 4 αποτελούν παραδείγματα υψηλής πυρηνικότητας και συμμετρίας πλειάδων του Mn, με αισθητικά όμορφες δομές και ενδιαφέρουσες μαγνητικές ιδιότητες. The synthesis and characterization of polynuclear metal complexes (clusters) containing paramagnetic 3d-metal ions in intermediate oxidation states have gained intense interest due to the applications of these compounds in several fields of science, such as bioinorganic chemistry, materials science, molecular physics and electronics, and theoretical chemistry. Such high nuclearity transition metal clusters are one of the growing research subjects in Molecular Magnetism, given the fact that they often possess a fairly large ground-state spin value, which is one of the necessary requirements for a molecule to be able to exhibit the phenomenon of single-molecule magnetism. In the present work, we studied the general reaction system manganese/2-(hydroxymethyl)pyridine (hmpH), in the presence or absence of cyanate ions (OCN-), under basic conditions, which has led to the isolation, and structural (through single-crystal X-ray crystallography) and magnetochemical characterization of the compounds [Mn7(OH)3(OCN)3(hmp)9](ClO4)2 (1), [Mn16O8(OMe)4(OCN)4(O2CMe)12(hmp)6(MeOH)2] (2), [Mn18O14(O2CMe)18(hmp)4(hmpH)2(H2O)2] (3) and [Mn18O14(O2CEt)18(hmp)4(hmpH)2(H2O)2] (4). All complexes 1-4 are mixed-valent (II/III). Complex 1 is a new member of a growing family of heptanuclear clusters with a core consisting of six Mn ions arranged in a ring around a seventh central Mn2+ ion. Complexes 2, 3 and 4 are examples of high-nuclearity and high-symmetry Mn clusters with aesthetically pleasing structures and interesting magnetic properties.