People from Brač, emigrant press in Chile and newspaper Domovina - from the late 19th century to the beginning of World War I

Cilj je rada postaviti ishodišta za proučavanje povijesti hrvatskog iseljeničkog novinstva u Čileu od najranijeg razdoblja doseljenja Hrvata do kraja 1914. godine, među kojima je brojčano dominantnu grupaciju činilo stanovništvo s Brača. Radilo se prvenstveno o ekonomskoj migraciji uzrokovanoj ekonomskim promjenama u društvu općenito, ali i ekonomskim promjenama kao posljedicama političkih kretanja. U novu domovinu donose tradicionalnu potrebu organiziranja u razna društva, ali i svijest o vlastitoj nacionalnoj pripadnosti s vlastitim jezikom. Neobično brza asimilacija (već u prvoj generaciji) dovodi u pitanje opstojnost te potrebu očuvanja baštine. Iseljeničke novine u kojima surađuju, uređuju ih i pokreću Bračani – novinari, među kojima se ističu Ivan Krstulović i Luka Bonačić s novinama „Domovina“ iz Punta Arenasa, u dosadašnjoj literaturi sagledavane su gotovo isključivo s aspekta političke orijentacije i borbe. Cilj je rada kroz primjer rubrike „Iz mjesta i okolice“, koja je održala kontinuitet tijekom cijelog razdoblja izlaženja lista „Domovina“ i čijim je sastavnim dijelom bila, prikazati, s aspekta socijalne povijesti, da su lokalne novine odražavale i bilježile pojave i događanja značajna za svakodnevni život zajednice sa svrhom očuvanja njezina identiteta.The topic of this paper is to set the starting point for studying the history of Croatian emigrant journalism in Chile from the earliest period of the settlement of Croats until the end of 1914, including the dominant population group from Brač. It was primarily the economic migration, which was caused by economic changes in the society in general, and economic changes as a consequence of political movements. The immigrants had the need for organizing themselves in various societies in the new country, and they also had the awareness of their own nationality and language. The unusually rapid assimilation (already in the first generation) calls into question the viability and the need to preserve heritage. Immigrant newspapers edited and run by Brač emigrant journalists, most notably Ivan Krstulović and Luka Bonačić, with the newspaper Domovina from Punta Arenas, were in the current literature perceived almost exclusively in terms of political orientation and struggle. The aim of this paper is to show that the local newspaper Domovina reflected and recorded phenomena and events significant for the daily life of the community with the intention of preservation its identity from the perspective of social history, especially in the section From the town and surrounding areas

Exchange Coupling and Magnetic Blocking in Bipyrimidyl Radical-Bridged Dilanthanide Complexes

The synthesis and magnetic properties of three new bipyrimidyl radical-bridged dilanthanide complexes, [(Cp*₂Ln)₂(μ-bpym^•)]⁺ (Ln = Gd, Tb, Dy), are reported. Strong Ln^III-bpym^•– exchange coupling is observed for all species, as indicated by the increases in χ_M<i>T</i> at low temperatures. For the Gd^III-containing complex, a fit to the data reveals antiferromagnetic coupling with <i>J</i> = −10 cm^–1 to give an <i>S</i> = ¹³/₂ ground state. The Tb^III and Dy^III congeners show single-molecule magnet behavior with relaxation barriers of <i>U</i>_eff = 44(2) and 87.8(3) cm^–1, respectively, a consequence of the large magnetic anisotropies imparted by these ions. Significantly, the latter complex exhibits a divergence of the field-cooled and zero-field-cooled dc susceptibility data at 6.5 K and magnetic hysteresis below this temperature

Exchange Coupling and Magnetic Blocking in Bipyrimidyl Radical-Bridged Dilanthanide Complexes

The synthesis and magnetic properties of three new bipyrimidyl radical-bridged dilanthanide complexes, [(Cp*₂Ln)₂(μ-bpym^•)]⁺ (Ln = Gd, Tb, Dy), are reported. Strong Ln^III-bpym^•– exchange coupling is observed for all species, as indicated by the increases in χ_M<i>T</i> at low temperatures. For the Gd^III-containing complex, a fit to the data reveals antiferromagnetic coupling with <i>J</i> = −10 cm^–1 to give an <i>S</i> = ¹³/₂ ground state. The Tb^III and Dy^III congeners show single-molecule magnet behavior with relaxation barriers of <i>U</i>_eff = 44(2) and 87.8(3) cm^–1, respectively, a consequence of the large magnetic anisotropies imparted by these ions. Significantly, the latter complex exhibits a divergence of the field-cooled and zero-field-cooled dc susceptibility data at 6.5 K and magnetic hysteresis below this temperature

Exchange Coupling and Magnetic Blocking in Bipyrimidyl Radical-Bridged Dilanthanide Complexes

The synthesis and magnetic properties of three new bipyrimidyl radical-bridged dilanthanide complexes, [(Cp*₂Ln)₂(μ-bpym^•)]⁺ (Ln = Gd, Tb, Dy), are reported. Strong Ln^III-bpym^•– exchange coupling is observed for all species, as indicated by the increases in χ_M<i>T</i> at low temperatures. For the Gd^III-containing complex, a fit to the data reveals antiferromagnetic coupling with <i>J</i> = −10 cm^–1 to give an <i>S</i> = ¹³/₂ ground state. The Tb^III and Dy^III congeners show single-molecule magnet behavior with relaxation barriers of <i>U</i>_eff = 44(2) and 87.8(3) cm^–1, respectively, a consequence of the large magnetic anisotropies imparted by these ions. Significantly, the latter complex exhibits a divergence of the field-cooled and zero-field-cooled dc susceptibility data at 6.5 K and magnetic hysteresis below this temperature

Exchange Coupling and Magnetic Blocking in Bipyrimidyl Radical-Bridged Dilanthanide Complexes

The synthesis and magnetic properties of three new bipyrimidyl radical-bridged dilanthanide complexes, [(Cp*₂Ln)₂(μ-bpym^•)]⁺ (Ln = Gd, Tb, Dy), are reported. Strong Ln^III-bpym^•– exchange coupling is observed for all species, as indicated by the increases in χ_M<i>T</i> at low temperatures. For the Gd^III-containing complex, a fit to the data reveals antiferromagnetic coupling with <i>J</i> = −10 cm^–1 to give an <i>S</i> = ¹³/₂ ground state. The Tb^III and Dy^III congeners show single-molecule magnet behavior with relaxation barriers of <i>U</i>_eff = 44(2) and 87.8(3) cm^–1, respectively, a consequence of the large magnetic anisotropies imparted by these ions. Significantly, the latter complex exhibits a divergence of the field-cooled and zero-field-cooled dc susceptibility data at 6.5 K and magnetic hysteresis below this temperature

Millisecond Coherence Time in a Tunable Molecular Electronic Spin Qubit

Quantum information processing (QIP) could revolutionize areas ranging from chemical modeling to cryptography. One key figure of merit for the smallest unit for QIP, the qubit, is the coherence time (<i>T</i>₂), which establishes the lifetime for the qubit. Transition metal complexes offer tremendous potential as tunable qubits, yet their development is hampered by the absence of synthetic design principles to achieve a long <i>T</i>₂. We harnessed molecular design to create a series of qubits, (Ph₄P)₂[V­(C₈S₈)₃] (<b>1</b>), (Ph₄P)₂[V­(β-C₃S₅)₃] (<b>2</b>), (Ph₄P)₂[V­(α-C₃S₅)₃] (<b>3</b>), and (Ph₄P)₂[V­(C₃S₄O)₃] (<b>4</b>), with <i>T</i>₂s of 1–4 μs at 80 K in protiated and deuterated environments. Crucially, through chemical tuning of nuclear spin content in the vanadium­(IV) environment we realized a <i>T</i>₂ of ∼1 ms for the species (<i>d</i>₂₀-Ph₄P)₂[V­(C₈S₈)₃] (<b>1</b>′) in CS₂, a value that surpasses the coordination complex record by an order of magnitude. This value even eclipses some prominent solid-state qubits. Electrochemical and continuous wave electron paramagnetic resonance (EPR) data reveal variation in the electronic influence of the ligands on the metal ion across <b>1</b>–<b>4</b>. However, pulsed measurements indicate that the most important influence on decoherence is nuclear spins in the protiated and deuterated solvents utilized herein. Our results illuminate a path forward in synthetic design principles, which should unite CS₂ solubility with nuclear spin free ligand fields to develop a new generation of molecular qubits

A Mononuclear Transition Metal Single-Molecule Magnet in a Nuclear Spin-Free Ligand Environment

The high-spin pseudotetrahedral complex [Co­(C₃S₅)₂]^2– exhibits slow magnetic relaxation in the absence of an applied dc magnetic field, one of a small number of mononuclear complexes to display this property. Fits to low-temperature magnetization data indicate that this single-molecule magnet possesses a very large and negative axial zero-field splitting and small rhombicity. The presence of single-molecule magnet behavior in a zero-nuclear spin ligand field offers the opportunity to investigate the potential for this molecule to be a qubit, the smallest unit of a quantum information processing (QIP) system. However, simulations of electron paramagnetic resonance (EPR) spectra and the absence of EPR spectra demonstrate that this molecule is unsuitable as a qubit due to the same factors that promote single molecule magnet behavior. We discuss the influence of rhombic and axial zero-field splitting on QIP applications and the implications for future molecular qubit syntheses

Determination of d‑Orbital Populations in a Cobalt(II) Single-Molecule Magnet Using Single-Crystal X‑ray Diffraction

The tetrahedral cobalt­(II) compound (Ph₄P)₂[Co­(SPh)₄] was the first mononuclear transition-metal complex shown to exhibit slow relaxation of the magnetization in zero external magnetic field. Because the relative populations of the d orbitals play a vital role in dictating the magnitude of the magnetic anisotropy, the magnetic behavior of this complex is directly related to its electronic structure, yet the exact role of the soft, thiophenolate ligands in influencing the d-electron configuration has previously only been investigated via theoretical methods. To provide detailed experimental insight into the effect of this ligand field, the electron density distribution in this compound was determined from low-temperature, single-crystal X-ray diffraction data and subsequent multipole modeling. Topological analysis of the electron density indicates significant covalent contributions to the cobalt–sulfur bonds. The derived d-orbital populations further reveal a fully occupied d_<i>z</i>² orbital, minor d_<i>xz</i> orbital population, and nearly equal population of the d_<i>xy</i>, d_<i>x</i>²_{–<i>y</i>²}, and d_<i>yz</i> orbitals. Notably, we find that an electrostatic interaction between Co­(II) and one hydrogen atom from a thiophenolate group in the <i>xz</i> plane increases the energy of the d_<i>x</i>²_{–<i>y</i>²} orbital, leading to the nearly equal population with d_<i>xy</i> and strong magnetic anisotropy

Employing Forbidden Transitions as Qubits in a Nuclear Spin-Free Chromium Complex

The implementation of quantum computation (QC) would revolutionize scientific fields ranging from encryption to quantum simulation. One intuitive candidate for the smallest unit of a quantum computer, a qubit, is electronic spin. A prominent proposal for QC relies on high-spin magnetic molecules, where multiple transitions between the many <i>M</i>_<i>S</i> levels are employed as qubits. Yet, over a decade after the original notion, the exploitation of multiple transitions within a single manifold for QC remains unrealized in these high-spin species due to the challenge of accessing forbidden transitions. To create a proof-of-concept system, we synthesized the novel nuclear spin-free complex [Cr­(C₃S₅)₃]^3– with precisely tuned zero-field splitting parameters that create two spectroscopically addressable transitions, with one being a forbidden transition. Pulsed electron paramagnetic resonance (EPR) measurements enabled the investigation of the coherent lifetimes (<i>T</i>₂) and quantum control (Rabi oscillations) for two transitions, one allowed and one forbidden, within the <i>S</i> = ³/₂ spin manifold. This investigation represents a step forward in the development of high-spin species as a pathway to scalable QC systems within magnetic molecules

Influence of Electronic Spin and Spin–Orbit Coupling on Decoherence in Mononuclear Transition Metal Complexes

Enabling the rational synthesis of molecular candidates for quantum information processing requires design principles that minimize electron spin decoherence. Here we report a systematic investigation of decoherence via the synthesis of two series of paramagnetic co­or­din­ation complexes. These complexes, [M­(C₂O₄)₃]^3– (M = Ru, Cr, Fe) and [M­(CN)₆]^3– (M = Fe, Ru, Os), were prepared and interrogated by pulsed electron paramagnetic resonance (EPR) spectroscopy to assess quantitatively the influence of the magnitude of spin (<i>S</i> = ¹/₂, ³/₂, ⁵/₂) and spin–orbit coupling (ζ = 464, 880, 3100 cm^–1) on quantum decoherence. Coherence times (<i>T</i>₂) were collected via Hahn echo experiments and revealed a small dependence on the two variables studied, demonstrating that the magnitudes of spin and spin–orbit coupling are not the primary drivers of electron spin decoherence. On the basis of these conclusions, a proof-of-concept molecule, [Ru­(C₂O₄)₃]³⁻, was selected for further study. The two parameters establishing the viability of a qubit are a long coherence time, <i>T</i>₂, and the presence of Rabi oscillations. The complex [Ru­(C₂O₄)₃]^3– exhibits both a coherence time of <i>T</i>₂ = 3.4 μs and the rarely observed Rabi oscillations. These two features establish [Ru­(C₂O₄)₃]^3– as a molecular qubit candidate and mark the viability of coordination complexes as qubit platforms. Our results illustrate that the design of qubit candidates can be achieved with a wide range of paramagnetic ions and spin states while preserving a long-lived coherence