Phospholyl and Arsolyl Triple-Decker Sandwich Complexes of Europium(II) and Strontium(II).

To study the influence of heteroatoms on the photophysical properties of divalent Eu and Sr complexes, the synthesis of the phospholyl and arsolyl compounds [{(Dtp)(thf)M}2{µ-η8:η8-C8H8}] (M = EuII and SrII; Dtp = 3,4-dimethyl-2,5-bis(tert-butyl)phospholyl) and [{(Dtas)(thf)M}2{µ-η8:η8-C8H8}] (M = EuII and SrII; Dtas = 3,4-dimethyl-2,5-bis(tert-butyl)arsolyl) is reported. Organometallic compounds of divalent europium with P and As heterocyclic ligands have not been described previously. They were prepared by salt elimination reactions from potassium phospholyl or arsolyl, K2C8H8, and EuI2(thf)2 or SrI2. Photophysical properties were investigated alongside a reference cyclopentadienyl complex with a comparable structure. Critically, the influence of the heteroatom on the photoluminescence emission and excitation and quantum yields of the complexes is significant. Density functional theory calculations were performed to rationalize the ligand influences.

Paramagnetic Nuclear Magnetic Resonance Shifts for Triplet Systems and Beyond with Modern Relativistic Density Functional Methods.

An efficient framework for the calculation of paramagnetic NMR (pNMR) shifts within exact two-component (X2C) theory and (current-dependent) density functional theory (DFT) up to the class of local hybrid functionals (LHFs) is presented. Generally, pNMR shifts for systems with more than one unpaired electron depend on the orbital shielding contribution and a temperature-dependent term. The latter includes zero-field splitting (ZFS), hyperfine coupling (HFC), and the g-tensor. For consistency, we calculate these three tensors at the same level of theory, i.e., using scalar-relativistic X2C augmented with spin-orbit perturbation theory. Results for pNMR chemical shifts of transition-metal complexes reveal that this X2C-DFT framework can yield good results for both the shifts and the individual tensor contributions of metallocenes and related systems, especially if the HFC constant is large. For small HFC constants, the relative error is often large, and sometimes the sign may be off. 4d and 5d complexes with more complicated structures demonstrate the limitations of a fully DFT-based approach. Additionally, a Co-based complex with a very large ZFS and pronounced multireference character is not well described. Here, a hybrid DFT-multireference framework is necessary for accurate results. Our results show that X2C is sufficient to describe relativistic effects and computationally cheaper than a fully relativistic approach. Thus, it allows use of large basis sets for converged HFCs. Overall, current-dependent meta-generalized gradient approximations and LHFs show some potential; however, the currently available functionals leave a lot to be desired, and the predictive power is limited.

Synthesis and properties of cyclic sandwich compounds.

Cyclic nanometre-scale sandwich complexes assembled from individual building blocks were synthesized. Sandwich complexes, in which a metal ion is π-coordinated by two planar aromatic organic rings belong to the foundations of organometallic chemistry. They have been successfully used in a wide variety of applications ranging from catalysis, synthesis and electrochemistry to nanotechnology, materials science and medicine1,2. Extending the sandwich structural motif leads to linear multidecker compounds, in which aromatic organic rings and metal atoms are arranged in an alternating fashion. However, the extension to a cyclic multidecker scaffold is unprecedented. Here we show the design, synthesis and characterization of an isomorphous series of circular sandwich compounds, for which the term 'cyclocenes' is suggested. These cyclocenes consist of 18 repeating units, forming almost ideally circular, closed rings in the solid state, that can be described by the general formula [cyclo-MII(µ-η8:η8-CotTIPS)]18 (M = Sr, Sm, Eu; CotTIPS = 1,4-(iPr3Si)2C8H62-). Quantum chemical calculations lead to the conclusion that a unique interplay between the ionic metal-to-ligand bonds, the bulkiness of the ligand system and the energy gain on ring closure, which is crucially influenced by dispersion interactions, facilitate the formation of these cyclic systems. Up to now, only linear one-dimensional multidecker sandwich compounds have been investigated for possible applications such as nanowires3-10. This textbook example of cyclic sandwich compounds is expected to open the door for further innovations towards new functional organometallic materials.

TURBOMOLE: Today and Tomorrow.

TURBOMOLE is a highly optimized software suite for large-scale quantum-chemical and materials science simulations of molecules, clusters, extended systems, and periodic solids. TURBOMOLE uses Gaussian basis sets and has been designed with robust and fast quantum-chemical applications in mind, ranging from homogeneous and heterogeneous catalysis to inorganic and organic chemistry and various types of spectroscopy, light-matter interactions, and biochemistry. This Perspective briefly surveys TURBOMOLE's functionality and highlights recent developments that have taken place between 2020 and 2023, comprising new electronic structure methods for molecules and solids, previously unavailable molecular properties, embedding, and molecular dynamics approaches. Select features under development are reviewed to illustrate the continuous growth of the program suite, including nuclear electronic orbital methods, Hartree-Fock-based adiabatic connection models, simplified time-dependent density functional theory, relativistic effects and magnetic properties, and multiscale modeling of optical properties.

Fully Tin-Coated Coinage Metal Ions: A Pincer-Type Bis-stannylene Ligand for Exclusive Tetrahedral Complexation.

Invited for the cover of this issue are the groups of P. W. Roesky (Karlsruhe) and F. Weigend (Marburg). The image depicts coinage metal cores with tetrahedrally coordinating tin atoms. Read the full text of the article at 10.1002/chem.202203583.

Ferrocene-driven single-chain polymer compaction.

We introduce single-chain nanoparticles (SCNPs) exclusively folded by covalently bonded ferrocene units. Specifially, we demonstrate the ability of 2-ferrocenyl-1,10-phenanthroline to fuse single-chain collapse with the concomitant introduction of a donor functionality allowing the installation of a Pd-catalytic site, affording the first heterobimetallic ferrocene-functionalized SCNP.

Fully Tin-Coated Coinage Metal Ions: A Pincer-Type Bis-stannylene Ligand for Exclusive Tetrahedral Complexation.

The synthesis of a novel bis-stannylene pincer ligand and its complexation with coinage metals (CuI , AgI and AuI ) are described. All coinage metal centres are in tetrahedral coordination environments in the solid state and are exclusively coordinated by four neutral SnII donors. 119 Sn NMR provided information about the behaviour in solution. All of the isolated compounds have photoluminescent properties, and these were investigated at low and elevated temperatures. Compared to the free bis-stannylene ligand, coordination to coinage metals led to an increase in the luminescence intensity. The new compounds were investigated in detail through all-electron relativistic density functional theory (DFT) calculations.

Introduction of plumbole to f-element chemistry.

Herein, we present the synthesis and characterization of heteroleptic lanthanide complexes bearing a dianionic η5-plumbole ligand in their coordination sphere. The reaction proceeds via a salt elimination reaction between the dilithioplumbole ([Li(thf)]2[1,4-bis-tert-butyl-dimethylsilyl-2,3-bis-phenyl-plumbolyl] = [Li2(thf)2(η5-LPb)]) and specifically designed [Ln(η8-COTTIPS)BH4] precursors (Ln = lanthanide, La, Ce, Sm, Er; COTTIPS = 1,4-bis-triisopropylsilyl-cyclooctatetraenyl), that are capable of stabilizing a planar plumbole moiety in the coordination sphere of different trivalent lanthanide ions. In-depth ab initio calculations show that the aromaticity of the dianionic plumbole is retained upon coordination. Electron delocalization occurs from the plumbole HOMO to an orbital of mainly d-character at the lanthanide ion. The magnetic properties of the erbium congener were investigated in detail, leading to the observation of magnetic hysteresis up to 5 K (200 Oe s-1), an unequivocal proof for single molecule magnet behavior in this system. The magnetic behavior of the erbium species can be modulated by manipulating the position of the lithium cation in the complex, which directly influences the bonding metrics in the central [(η5-LPb)Er(η8-COTTIPS)]- fragment. This allowed us to assess a fundamental magneto-structural correlation in an otherwise identical inner coordination sphere.

Paramagnetic NMR Shielding Tensors and Ring Currents: Efficient Implementation and Application to Heavy Element Compounds.

We present an efficient implementation of paramagnetic NMR shielding tensors and shifts in a nonrelativistic and scalar-relativistic density functional theory framework. For the latter, we make use of the scalar exact two-component Hamiltonian in its local approximation, and generally we apply the well established (multipole-accelerated) resolution of the identity approximation and the seminumerical exchange approximation. The perturbed density matrix of a paramagnetic NMR shielding calculation is further used to study the magnetically induced current density and ring currents of open-shell systems as illustrated for [U@Bi12]3-. [U@Bi12]3- features delocalized highest occupied molecular orbitals and sustains a net diatropic ring current of ca. 18 nA/T through the Bi12 torus similar to the all-metal aromatic heavy-element cluster [Th@Bi12]4-.