Application of the Adiabatic Connection Random Phase Approximation to Electron-Nucleus Hyperfine Coupling Constants.

The electron-nucleus hyperfine coupling constant is a challenging property for density functional methods. For accurate results, hybrid functionals with a large amount of exact exchange are often needed and there is no clear "one-for-all" functional which describes the hyperfine coupling interaction for a large set of nuclei. To alleviate this unfavorable situation, we apply the adiabatic connection random phase approximation (RPA) in its post-Kohn-Sham fashion to this property as a first test. For simplicity, only the Fermi-contact and spin-dipole terms are calculated within the nonrelativistic and the scalar-relativistic exact two-component framework. This requires to solve a single coupled-perturbed Kohn-Sham equation to evaluate the relaxed density matrix, which comes with a modest increase in computational demands. RPA performs remarkably well and substantially improves upon its Kohn-Sham (KS) starting point while also reducing the dependence on the KS reference. For main-group systems, RPA outperforms global, range-separated, and local hybrid functionals─at similar computational costs. For transition-metal compounds and lanthanide complexes, a similar performance as for hybrid functionals is observed. In contrast, related post-Hartree-Fock methods such as Møller-Plesset perturbation theory or CC2 perform worse than semilocal density functionals.

Dye induced luminescence properties of gold(I) complexes with near unity quantum efficiency.

To study the effect of a dye on the photoluminescence (PL) properties of metal complexes, a series of gold(I) complexes were synthesized, containing a 7-amino-4-methylcoumarin luminophore. The complexes are comprised of a coumarin moiety featuring different ancillary ligands, specifically N-heterocyclic carbenes, triphenylphosphine, and diphenyl-2-pyridylphosphine. The synthesized gold(I) complexes are luminescent both in solution and the solid state at room temperature and 77 K. Complexes of different nuclearity, i.e., mono-, di- and trinuclear compounds were synthesized. A clear trend between the nuclearity and the quantum yields can be seen. The coumarin dye not only improves the PL properties, but also enhances the luminescence of trinuclear clusters, which are otherwise known to be weak emitters in solution. The optical absorption properties were investigated in detail by quantum chemical calculations.

Thiocarbonyl Pseudohalides - The Curious Case of Thiocarbonyl Dithiocyanate.

Thiocarbonyl dithiocyanate (1) and chlorothiocarbonyl thiocyanate (2) were synthesized from thiophosgene and ammonium or silver thiocyanate, respectivley. Their crystal structures show syn-anti (1) and syn (2) conformations, which were confirmed in the bulk phases by powder X-ray diffraction, vibrational spectroscopy and DFT calculations. Further calculations explain the isolation of the kinetic reaction products by a lower transition states opposed to the thermodynamic reaction products. Reaction of 1 with ethanol gave a dithiobiuret derivative (3). In a proof-of-principle study we show that it in turn can be used for the complexation of nickel to yield (4).

Supramolecular trapping of a cationic all-metal σ-aromatic {Bi4} ring.

Aromaticity in organic molecules is well defined, but its role in metal-only rings remains controversial. Here we introduce a supramolecular stabilization approach of a cationic {Bi4} rhomboid within the symmetric charge sphere of two bowl-shaped dianionic calix[4]pyrrolato indinates. Crystallographic and spectroscopic characterization, quantum chemical analysis and magnetically induced ring currents indicate σ-aromaticity in the formally tetracationic 16-valence electron [Bi4]4+ ring. Computational screening for other p-block elements identifies the planar rhomboid as the globally preferred structure for 16-valence electron four-atomic clusters. The aromatic [Bi4]4+ is isoelectronic to the [Al4]4-, a motif previously observed as antiaromatic in Li3[Al4]- in the gas phase. Thus, subtle factors such as charge isotropy seem to decide over aromaticity or antiaromaticity, advising for caution in debates based on the Hückel model-a concept valid for second-row elements but less deterministic for the heavier congeners.

[GeRu6(CO)18HI]: A Germanium-Centered Ruthenium Carbonyl Cluster with Aromatic Ring Current.

The carbonyl cluster compound [GeRu6(CO)18HI] is unique in regard to its structure and bonding with a GeRu6 cluster core, a planar GeRu4HI unit, extensive multi-center bonding, and an aromatic ring current similar to benzene (9-10 nA T-1). The open-shell cluster core is a Ge-centered five-membered Ru4(Ru2) ring with CO ligands and an additional H and I atom, each bridging two Ru atoms on opposite sides of the cluster core. The compound is prepared at 130 °C in a weakly-coordinating ionic liquid.

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.

Formation and Reactivity of heavy Group 14-15 bonds.

A series of low-valent Group 14-15 compounds were obtained starting from [(Dipp2 NacNac)MCl] (M=Ge-Pb) (I-III) (Dipp2 NacNac=HC{C(Me)N(Dipp)}2 ) and M'E(SiMe3 )2 (M'=Li, E=As; M'=K, E=Sb, Bi) (IV-VI). In the course of this investigations we were able to fully characterize all permutations except Pb-Bi for compounds of the composition [(Dipp2 NacNac)ME(SiMe3 )2 ] (1E : M=Ge, 2E : M=Sn, 3E : M=Pb). Thus, we report the first low valent tetrelene with Sn-Bi bond. All isolated compounds, were examined by NMR spectroscopy, IR spectroscopy and except compound 1As by X-ray structure analysis. Moreover, were examined UV-Vis spectroscopy and investigated the reactivity of these compounds towards different substrates in more detail. Starting with the compound [(Dipp2 NacNac)SnAs(SiMe3 )2 ] (2As ), the reaction with red selenium yields [(Dipp2 NacNac)Sn-Se-As(SiMe3 )2 ] (4) which exhibits a Sn-Se-As chain.

Zero-field splitting parameters within exact two-component theory and modern density functional theory using seminumerical integration.

An efficient implementation of zero-field splitting parameters based on the work of Schmitt et al. [J. Chem. Phys. 134, 194113 (2011)] is presented. Seminumerical integration techniques are used for the two-electron spin-dipole contribution and the response equations of the spin-orbit perturbation. The original formulation is further generalized. First, it is extended to meta-generalized gradient approximations and local hybrid functionals. For these functional classes, the response of the paramagnetic current density is considered in the coupled-perturbed Kohn-Sham equations for the spin-orbit perturbation term. Second, the spin-orbit perturbation is formulated within relativistic exact two-component theory and the screened nuclear spin-orbit (SNSO) approximation. The accuracy of the implementation is demonstrated for transition-metal and diatomic main-group compounds. The efficiency is assessed for Mn and Mo complexes. Here, it is found that coarse integration grids for the seminumerical schemes lead to drastic speedups while introducing clearly negligible errors. In addition, the SNSO approximation substantially reduces the computational demands and leads to very similar results as the spin-orbit mean field Ansatz.

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.

Double Addition vs. Ring Closure: Systematic Reactivity Study of CO(NCO)2 and CO(NCS)2 towards Hydrogen Halides.

The reactivity of carbonyl diisocyanate, CO(NCO)2 , and carbonyl diisothiocyanate, CO(NCS)2 with nucleophiles shows different patterns: Whereas carbonyl diisocyanate adds two equivalents of nucleophile forming carbonyl bis(carbamoylhalides), carbonyl diisothiocyanate only adds one equivalent and undergoes intramolecular ring closure, resulting in the formation of substituted thiadiazines. In this study we have reacted both carbonyl diisocyanate and carbonyl diisothiocyanate with the full series of hydrogen halides HF to HI, isolating carbonyl bis(carbamoylfluoride) (1), -chloride (2), -bromide (3), and -iodide (4) as well as (6-chloro-2,3-dihydro-2-thioxo-4H-1,3,5-thiadiazin-4-one (5), and 6-bromo-2,3-dihydro-2-thioxo-4H-1,3,5-thiadiazin-4-one (6). The compounds were analysed by single-crystal X-ray diffraction, NMR spectroscopy, IR and Raman spectroscopy, and elemental analysis. Quantum mechanical calculations show thermodynamic reasons for the differences in reactivity.

Ion-Selective Assembly of Supertetrahedral Selenido Germanate Clusters for Alkali Metal Ion Capture and Separation.

Supertetrahedral chalcogenido (semi)metalate cluster-based frameworks possess high selectivity for alkali metal cations, matching the specific charge density of their inner surfaces, which enables their use as ion-exchange materials. Aggregates of the supertetrahedral chalcogenido metalate cluster offer even new perspectives for metal ion capture and separation. Herein, we report on ionothermal preparation of two corresponding model compounds, (C2C1Im)7[Cs@GeII4(GeIV4Se10)4] (1) and (C2C1Im)10[Na5(CN)6@Cu6(Ge4Se10)4(Cu)] (2). Their formation is reliant on one specific cation type each, Cs+ for 1 and Na+ for 2, thus providing promising separation potential during crystallization. Compound 1 is based on the largest discrete binary selenido germanate cluster reported to date and the first mixed-valent chalcogenido germanate(II/IV) supertetrahedron. Moreover, it adds to the few examples of chalcogenides capable of capturing Cs+ ions. Its high selectivity for Cs+ compared to that of Li+, Na+, K+, and Rb+ was confirmed by single-crystal X-ray diffraction, energy-dispersive X-ray spectroscopy, and electrospray ionization mass spectrometry. Quantum chemical studies indicate that smaller ions, K+ and Rb+, could also be embedded in an isolated cluster assembly, but as the cluster aggregate slightly distorts for crystallization, the selectivity for Cs+ becomes exclusive in the salt. The anionic substructure of compound 2 is based on a two-dimensional network of supramolecular assemblies and exhibits an exclusive preference for Na+. This work thus provides the first comprehensive insight into the selective incorporation of specific alkali metal ions into supramolecular aggregates of supertetrahedral chalcogenide clusters, as a promising basis for new ion trapping techniques─especially for heavy alkali metal ions that pose environmental challenges.

Establishing Family Relations in Group 15 Halogenido Metalates with the Largest Molecular Antimony Iodide Anion.

Studying structurally related families of compounds is a valuable tool in understanding and predicting material properties and has been extensively used for metal halide perovskites. Due to the variable anion structures in group 15 halogenido metalates, similar family relations are still largely missing. Herein, we present compounds featuring the [Sb2n I6n+4 ]4- family of anions, including the first n=5 member in [Hpyz]4 [Sb10 I34 ] (Hpyz=pyrazinium), which contains the largest halogenido pentelate anion reported to date. The optical properties of compounds featuring n=1-5 anions show a clear trend as well as an outlier, a low band gap of 1.72 eV for [Hpyz]4 [Sb10 I34 ], that can be well understood using quantum chemical investigations. Also using SbI3 and [H2 NMe2 ]3 [SbI6 ], a compound featuring a single octahedral [SbI6 ]3- unit, as limiting cases, we show that structure-property relationships can be established in group 15 halogenido metalates in a similar way as in metal halide perovskites, thus providing a framework for understanding new and known compounds in this emerging class of materials.

[M@Sn14-xSbx]q- (M = La, Ce, or U; x = 6-8; q = 3, 4): Interaction of 4f or 5f Metal Ions with 5p Metal Atoms in Intermetalloid Clusters.

The impact of 4f metal ions Ln3+ (Ln = La or Ce) versus 5f metal ions Un+ (n = 3 or 4) on the compositions and distribution of 5p metal atoms in the cluster shells of endohedral species [M@Sn14-xSbx]q- (M = La, Ce, or U; x = 6-8; q = 3, 4) was studied by means of combined experimental and quantum chemical investigations. While all known f-block metal ion-centered endohedral clusters possessed combinations of larger main group metal atoms so far (Sn/Bi or Pb/Bi), resulting in mixtures of 13- and 14-atom cages, the 14-atom cages reported herein comprise exclusively Sn and Sb atoms and therefore are challenged in accommodating the large 4f and 5f ions. We show that the clusters form in reactions of (Sn2Sb2)2- anions with [Ln(C5Me4H)3] or [U(C5Me4H)3Cl], and that salts of [La@Sn6Sb8]3-, [La@Sn7Sb7]4-, [U@Sn8Sb6]4-, and [U@Sn7Sb7]3- can be isolated from them. The assignment of Sn versus Sb in the encapsulating cage follows a simple rule. Different central atoms cause only slight differences in this regard and with respect to distortions of the cluster shells. The reactions also yielded the salt of the new binary anion (Sn4Sb4)2- that was recently predicted by quantum chemical studies.

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.

Experimental and theoretical evidence for low-lying excited states in [Cr6E8(PEt3)6] (E = S, Se, Te) cluster molecules.

Three [Cr6E8(PEt3)6] cluster molecules with E = S, Se, and Te have been synthesized by reaction of stoichiometric mixtures of Cr(II) and Cr(III) metal salts with silylated chalcogen reagents E(SiMe3)2 (E = S, Se, Te) in the presence of L = PEt3 = triethylphosphine. For the sulfide- and selenide-bridged clusters two crystallographic forms (trigonal R3̄ and triclinic P1̄), which differ in the presence of lattice solvent molecules, have been isolated. Structural data, optical spectra and quantum chemical calculations reveal the presence of low-lying excited states in [Cr6E8(PEt3)6] (E = S, Se), which would help in rationalizing the non-vanishing magnetic moments at 2 K revealed by DC magnetic measurements and EPR spectroscopy. These findings are partially in contrast to a previous report by Saito and co-workers (S. Kamiguchi, H. Imoto, T. Saito, Inorg. Chem., 1998, 37, 6852-6857.), who postulated an incorporated hydrogen atom as the source of paramagnetism at low temperatures for the trigonal forms of [Cr6E8(PEt3)6] (E = S, Se).

Stimuli Responsive Silylene: Electromerism Induced Reversible Switching Between Mono- and Bis-Silylene.

Electromerism is a very well-known phenomenon in transition metal chemistry. In main group chemistry, this concept has only started getting attention recently. We report stimuli responsive low-valent silicon compounds exhibiting electromerism. A mixed-valent silaiminyl-silylene 1, [LSi-Si(NDipp)L] (L=PhC(Nt Bu)2 ), was synthesized in a single step from amidinate-chlorosilylene. Compound 1 has two interconnected Si atoms in formally +I and +III oxidation states. Upon treatment with Lewis acidic CuI X (X=mesityl, Cl, Br, I), electron redistribution occurs resulting in the formation of [{LSi(NDipp)Si(L)}-CuX], in which both silicon atoms are in the +II formal oxidation state. Removal of the copper center from [{LSi(NDipp)Si(L)}-CuX] by using a Lewis basic carbene led to reformation of the precursor [LSi-Si(NDipp)L]. Thus, the process is fully reversible. This showcases the first example of Lewis acid/base-induced reversible electromerism in silicon chemistry.

Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi3 )2- Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe3 )2 }2 ].

Lowering the charge of Zintl anions by (element-)organic substituents allows their use as sources of (semi)metal nanostructures in common organic solvents, as realized for group 15 anions or Ge9 4- and Sn9 4- . We developed a new strategy for other anions, using low-coordinate 3d metal complexes as electrophiles. [K(crypt-222)]+ salts of (TrBi3 )2- anions dissolved in situ in Et2 O and/or THF when reacted with [Mn(hmds)2 ]. Work-up afforded soluble [K(crypt-222)]+ salts of [{(hmds)2 Mn}2 (TlBi3 )]2- (in 1), [{(hmds)2 Mn}2 (Bi2 )]2- (in 2), and [{(hmds)Mn}4 (Bi2 )2 ]2- (in 3) (crypt-222=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane; Tr=Ga, In, Tl; hmds=N(SiMe3 )2 ), representing rare cases of Zintl clusters with open-shell metal atoms. 1 comprises the first coordination compound of the (TlBi3 )2- anion, 2 features a diamond-shaped {Pn2 M2 } unit, and 3 is a mixed-valent MnI /MnII compound. The uncommon electronic structures in 1-3 and magnetic coupling were studied by comprehensive DFT calculations.