Yb-to-Eu Cooperative Sensitization Upconversion in a Multifunctional Molecular Nonanuclear Lanthanide Cluster in Solution.

Lanthanide metal clusters excel in combining molecular and material chemistry properties. Here, we report an efficient cooperative sensitization UC phenomenon of a Eu3+/Yb3+ nonanuclear lanthanide cluster in CD3OD. The synthesis and characterization of the heteronuclear cluster in the solid state and solution are described together with the UC phenomenon showing Eu3+ luminescence in the visible region upon 980 nm NIR excitation of Yb3+ at concentrations as low as 100 nM. Alongside being the Eu/Yb cluster to display UC (with a quantum yield value of 4.88 × 10-8 upon 1.13 W cm-2 excitation at 980 nm), the cluster exhibits downshifted light emission of Yb3+ in the NIR region upon 578 nm visible excitation of Eu3+, which is ascribed to sensitization pathways for Yb through the 5D0 energy levels of Eu3+. Additionally, a faint emission is also observed at ca. 500 nm upon 980 nm excitation, originating from the cooperative luminescence of Yb3+. The [Eu8Yb(BA)16(OH)10]Cl cluster (BA = benzoylacetonate) is also a field-induced single-molecular magnet (SMM) under 4K with a modest Ueff/kB of 8.48 K, thereby joining the coveted list of Yb-SMMs and emerging as a prototype system for next-generation devices, combining luminescence with single-molecular magnetism in a molecular cluster.

Unconventional Band Structure via Combined Molecular Orbital and Lattice Symmetries in a Surface-Confined Metallated Graphdiyne Sheet.

Graphyne (GY) and graphdiyne (GDY)-based monolayers represent the next generation 2D carbon-rich materials with tunable structures and properties surpassing those of graphene. However, the detection of band formation in atomically thin GY/GDY analogues has been challenging, as both long-range order and atomic precision have to be fulfilled in the system. The present work reports direct evidence of band formation in on-surface synthesized metallated Ag-GDY sheets with mesoscopic (≈1 µm) regularity. Employing scanning tunneling and angle-resolved photoemission spectroscopies, energy-dependent transitions of real-space electronic states above the Fermi level and formation of the valence band are respectively observed. Furthermore, density functional theory (DFT) calculations corroborate the observations and reveal that doubly degenerate frontier molecular orbitals on a honeycomb lattice give rise to flat, Dirac and Kagome bands close to the Fermi level. DFT modeling also indicates an intrinsic band gap for the pristine sheet material, which is retained for a bilayer with h-BN, whereas adsorption-induced in-gap electronic states evolve at the synthesis platform with Ag-GDY decorating the (111) facet of silver. These results illustrate the tremendous potential for engineering novel band structures via molecular orbital and lattice symmetries in atomically precise 2D carbon materials.

Altering Spin Distribution of Tb2Pc3 via Molecular Chirality Manipulation.

Manipulating the chirality of the spin-polarized electronic state is pivotal for understanding many unusual quantum spin phenomena, but it has not been achieved at the single-molecule level. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we successfully manipulate the chirality of spin distribution in a triple-decker single-molecule magnet tris(phthalocyaninato)bis(terbium(III)) (Tb2Pc3), which is evaporated on a Pb(111) substrate via molecular beam epitaxy. The otherwise achiral Tb2Pc3 becomes chiral after being embedded into the self-assembled monolayer films of bis(phthalocyaninato)terbium(III) (TbPc2). The chirality of the spin distribution in Tb2Pc3 is manifested via the spatial mapping of its Kondo resonance state from its ligand orbital. Our first-principles calculations revealed that the spin and molecular chirality are associated with a small rotation followed by a structural distortion of the top Pc, consistent with the experimental observation. By constructing tailored molecular clusters with the STM tip, a single Tb2Pc3 molecule can be manipulated among achiral and differently handed chiral configurations of spin distributions reversibly. This paves the way for designing chiral spin enantiomers for fundamental studies and developing functional spintronic devices.

Hierarchical Self-Assembly and Conformation of Tb Double-Decker Molecular Magnets: Experiment and Molecular Dynamics.

Nanostructures, fabricated by locating molecular building blocks in well-defined positions, for example, on a lattice, are ideal platforms for studying atomic-scale quantum effects. In this context, STM data obtained from self-assembled Bis(phthalocyaninato) Terbium (III) (TbPc2) single-molecule magnets on various substrates have raised questions about the conformation of the TbPc2 molecules within the lattice. In order to address this issue, molecular dynamics simulations were carried out on a 2D assembly of TbPc2 molecules. The calculations are in excellent agreement with the experiment, and thus improve our understanding of the self-assembly process. In particular, the calculated electron density of the molecular assembly compares well with STM contrast of self-assembled TbPc2 on Au(111), simultaneously providing the conformation of the two Pc ligands of the individual double-decker molecule. This approach proves valuable in the identification of the STM contrast of LnPc2 layers and could be used in similar cases where it is difficult to interpret the STM images of an assembly of molecular complexes.

Long Cycle-Life Ca Batteries with Poly(anthraquinonylsulfide) Cathodes and Ca-Sn Alloy Anodes.

Calcium (Ca) batteries are attractive post-lithium battery technologies, due to their potential to provide high-voltage and high-energy systems in a sustainable manner. We investigated herein 1,5-poly(anthraquinonylsulfide) (PAQS) for Ca-ion storage with calcium tetrakis(hexafluoroisopropyloxy)borate Ca[B(hfip)4 ]2 [hfip=OCH(CF3 )2 ] electrolytes. It is demonstrated that PAQS could be synthesized in a cost-effective approach and be processed environmentally friendly into the electrodes. The PAQS cathodes could provide 94 mAh g-1 capacity at 2.2 V vs. Ca at 0.5C (1C=225 mAh g-1 ). However, cycling of the cells was severely hindered due to the fast degradation of the metal anode. Replacing the Ca metal anode with a calcium-tin (Ca-Sn) alloy anode, the PAQS cathodes exhibited long cycling performance (45 mAh g-1 at 0.5C after 1000 cycles) and superior rate capability (52 mAh g-1 at 5C). This is mainly ascribed to the flexible structure of PAQS and good compatibility of the alloy anodes with the electrolyte solutions, which allow reversible quinone carbonyl redox chemistry in the Ca battery systems. The promising properties of PAQS indicate that further exploration of the organic cathode materials could be a feasible direction towards green Ca batteries.

Molecular Engineering of Metalloporphyrins for High-Performance Energy Storage: Central Metal Matters.

Porphyrin derivatives represent an emerging class of redox-active materials for sustainable electrochemical energy storage. However, their structure-performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules. The A2 B2 -type porphyrin 5,15-bis(ethynyl)-10,20-diphenylporphyrin and its first-row transition metal complexes from Co to Zn are used as models to investigate the relationships between structure and electrochemical performance. It turned out that the choice of central metal atom has a profound influence on the practical voltage window and discharge capacity. The results of DFT calculations suggest that the choice of central metal atom triggers the degree of planarity of the porphyrin. Single crystal diffraction studies illustrate the consequences on the intramolecular rearrangement and packing of metalloporphyrins. Besides the direct effect of the metal choice on the undesired solubility, efficient packing and crystallinity are found to dictate the rate capability and the ion diffusion along with the porosity. Such findings open up a vast space of compositions and morphologies to accelerate the practical application of resource-friendly cathode materials to satisfy the rapidly increasing need for efficient electrical energy storage.

Spin-orbital Yu-Shiba-Rusinov states in single Kondo molecular magnet.

Studies of single-spin objects are essential for designing emergent quantum states. We investigate a molecular magnet Tb2Pc3 interacting with a superconducting Pb(111) substrate, which hosts unprecedented Yu-Shiba-Rusinov (YSR) subgap states, dubbed spin-orbital YSR states. Upon adsorption of the molecule on Pb, the degeneracy of its lowest unoccupied molecular orbitals (LUMO) is lifted, and the lower LUMO forms a radical spin via charge transfer. This leads to Kondo screening and subgap states. Intriguingly, the YSR states display two pairs of resonances with clearly distinct behavior. The energy of the inner pair exhibits prominent inter and intra molecular variation, and it strongly depends on the tip height. The outer pair, however, shifts only slightly. As is unveiled through theoretical calculations, the two pairs of YSR states originate from the ligand spin and charge-fluctuating higher LUMO, coexisting in a single molecule, but only weakly coupled presumably due to different spatial distribution. Our work paves the way for understanding complex many-body excitations and constructing molecule-based topological superconductivity.

Indirect Spin-Readout of Rare-Earth-Based Single-Molecule Magnet with Scanning Tunneling Microscopy.

Rare-earth based single-molecule magnets are promising candidates for magnetic information storage including qubits as their large magnetic moments are carried by localized 4f electrons. This shielding from the environment in turn hampers a direct electronic access to the magnetic moment. Here, we present the indirect readout of the Dy moment in Bis(phthalocyaninato)dysprosium (DyPc_{2}) molecules on Au(111) using milli-Kelvin scanning tunneling microscopy. Because of an unpaired electron on the exposed Pc ligand, the molecules show a Kondo resonance that is, however, split by the ferromagnetic exchange interaction between the unpaired electron and the Dy angular momentum. Using spin-polarized scanning tunneling spectroscopy, we read out the Dy magnetic moment as a function of the applied magnetic field, exploiting the spin polarization of the exchange-split Kondo state.

A Self-Conditioned Metalloporphyrin as a Highly Stable Cathode for Fast Rechargeable Magnesium Batteries.

Development of practical rechargeable Mg batteries (RMBs) is impeded by their limited cycle life and rate performance of cathodes. As demonstrated herein, a copper-porphyrin with meso-functionalized ethynyl groups is capable of reversible two- and four-electron storage at an extremely fast rate (tested up to 53 C). The reversible four-electron redox process with cationic-anionic contributions resulted in a specific discharge capacity of 155 mAh g-1 at the high current density of 1000 mA g-1 . Even at 4000 mA g-1 , it still delivered >70 mAh g-1 after 500 cycles, corresponding to an energy density of >92 Wh kg-1 at a high power of >5100 W kg-1 . The ability to provide such high-rate performance and long-life opens the way to the development of practical cathodes for multivalent metal batteries.

Pressure-Modulated Broadband Emission in 2D Layered Hybrid Perovskite-Like Bromoplumbate.

Two-dimensional (2D) layered hybrid bromoplumbate perovskites are promising candidates for solution-processed light-emitting materials. Here, we report the synthesis and characterization of two novel layered bromoplumbates: (4BrPhMA)2PbBr4 (1) and (4BrPhA)6Pb3Br12 (2), where 4BrPhMA is (4-bromophenyl)methylammonium and 4BrPhA is (4-bromophenyl) ammonium. Despite similar optical absorption, these materials show remarkably different photoluminescence properties: 1 emits a narrow exciton band at ca. 395 nm with a very small bandwidth (particularly at low temperatures of 15-50 K) and Stokes shift, while 2 exhibits a broad emission at ca. 560 nm with a large Stokes shift, both at low and ambient temperatures. However, under several kbar of hydrostatic pressure, the broad emission diminishes and a new band reversibly develops at ca. 395 nm, similar to that in 1. Our results emphasize organic layer flexibility as an important design factor for this class of perovskite-like materials featuring broadband emission.

Conductive Metal-Organic Framework Thin Film Hybrids by Electropolymerization of Monosubstituted Acetylenes.

1-Hexyne monomers were potentiostatically electropolymerized upon confinement in 1D channels of a surface-mounted metal-organic framework Cu(BDC) (SURMOF-2). A layer-by-layer deposition method allowed for SURMOF depostition on substrates with prepatterned electrodes, making it possible to characterize electrical conductivity in situ, i.e., without having to delaminate the conductive polymer thin film. Successful polymerization was evidenced by mass spectroscopy, and the electrical measurements demonstrated an increase of the electrical conductivity of the MOF material by 8 orders of magnitude. Extensive DFT calculations revealed that the final conductivity is limited by electron hopping between the conductive oligomers.

Understanding the Superior Stability of Single-Molecule Magnets on an Oxide Film.

The stability of magnetic information stored in surface adsorbed single-molecule magnets is of critical interest for applications in nanoscale data storage or quantum computing. The present study combines X-ray magnetic circular dichroism, density functional theory and magnetization dynamics calculations to gain deep insight into the substrate dependent relevant magnetization relaxation mechanisms. X-ray magnetic circular dichroism reveals the opening of a butterfly-shaped magnetic hysteresis of DyPc2 molecules on magnesium oxide and a closed loop on the bare silver substrate, while density functional theory shows that the molecules are only weakly adsorbed in both cases of magnesium oxide and silver. The enhanced magnetic stability of DyPc2 on the oxide film, in conjunction with previous experiments on the TbPc2 analogue, points to a general validity of the magnesium oxide induced stabilization effect. Magnetization dynamics calculations reveal that the enhanced magnetic stability of DyPc2 and TbPc2 on the oxide film is due to the suppression of two-phonon Raman relaxation processes. The results suggest that substrates with low phonon density of states are beneficial for the design of spintronics devices based on single-molecule magnets.

Screening the 4f-electron spin of TbPc2 single-molecule magnets on metal substrates by ligand channeling.

Bis(phthalocyaninato)lanthanide (LnPc2) double-decker-based devices have recently attracted a great deal of interest for data encoding purposes. Although the 4f-electrons of lanthanide ions play a key role in the experimental methodology, their localized character, deeper in energy compared to the 3d electrons of transition metals, hampers a detailed investigation. Here, our approach consists of the follow-up of the entanglement process with other molecules and with the substrate electrons by means of space-resolved detection of the Kondo resonance by scanning tunneling spectroscopy (STS), using different substrates (from weak to strong interaction). It is found that TbPc2 molecules firstly interact with their environment by means of the π-radicals of the ligand. The radical spin of TbPc2 can be identified by STS on a weakly interacting substrate such as Au(111). In the case of a Ag(111) substrate, we are able to analyze the effect of an electron transfer on the molecule (pairing-up of the radical spin) and the subsequent quenching of the Kondo resonance. Finally, on a strongly interacting substrate such as Cu(111), a significant rearrangement of electrons takes place and the Kondo screening of the 4f electrons of the Tb ion of TbPc2 is observed. By comparative STS measurements on YPc2, that has empty 4d and 4f shells, we prove that the Kondo resonance measured in the center of the TbPc2 molecule indeed stems from the 4f-electrons. At the same time, we provide evidence for the hybridization of the 4f states with the π electron.

A Lithium-Free Energy-Storage Device Based on an Alkyne-Substituted-Porphyrin Complex.

Porphyrin complexes are well-known for their application in solar-cell systems and as catalysts; however, their use in electrochemical energy-storage applications has scarcely been studied. Here, a tetra-alkenyl-substituted [5,10,15,20-tetra(ethynyl)porphinato]copper(II) (CuTEP) complex was used as anode material in a high-performance lithium-free CuTEP/PP14 TFSI/graphite cell [PP14 TFSI=1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide]. Thereby, the influence of size and morphology on the electrochemical performance of the cell was thoroughly investigated. Three different nanocrystal CuTEP morphologies, namely nanobricks, nanosheets, and nanoribbons, were studied as anode material, and the best cyclability and highest rate capability were obtained for the nanoribbon samples. A high specific power density of 14 kW kg-1 (based on active material) and excellent rechargeability were achieved with negligible capacity decay over 1000 cycles at a high current density of 5 A g-1 . These results indicate that the porphyrin complex CuTEP could be a promising electrode material in high-performance lithium-free batteries.

Quantum Tunneling Mediated Interfacial Synthesis of a Benzofuran Derivative.

Reaction pathways involving quantum tunneling of protons are fundamental to chemistry and biology. They are responsible for essential aspects of interstellar synthesis, the degradation and isomerization of compounds, enzymatic activity, and protein dynamics. On-surface conditions have been demonstrated to open alternative routes for organic synthesis, often with intricate transformations not accessible in solution. Here, we investigate a hydroalkoxylation reaction of a molecular species adsorbed on a Ag(111) surface by scanning tunneling microscopy complemented by X-ray electron spectroscopy and density functional theory. The closure of the furan ring proceeds at low temperature (down to 150 K) and without detectable side reactions. We unravel a proton-tunneling-mediated pathway theoretically and confirm experimentally its dominant contribution through the kinetic isotope effect with the deuterated derivative.

Surface-Dependent Chemoselectivity in C-C Coupling Reactions.

Surface-confined covalent coupling reactions of the linear compound 4-(but-3-en-1-ynyl)-4'-ethynyl-1,1'-biphenyl (1), which contains one alkyne and one enyne group on opposing ends, have been investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The reactions show a surface-dependent chemoselectivity: on Au(111), compound 1 preferentially yields cyclotrimerization products, while on Cu(111), a selective coupling between the enyne and alkyne groups is observed. Linear, V-shaped string formations combined with Y-shaped bifurcation motifs result in a random reticulation on the entire surface. DFT calculations show that the C-H⋅⋅⋅πδ- transition state of the reaction between the deprotonated alkyne group and a nearby H-donor of the alkene group plays a key role in the mechanism and high chemoselectivity. This study highlights a concept that opens new avenues to the surface-confined synthesis of covalent carbon-based sp-sp2 polymers.

Synthesizing Highly Regular Single-Layer Alkynyl-Silver Networks at the Micrometer Scale via Gas-Mediated Surface Reaction.

Extended organometallic honeycomb alkynyl-silver networks have been synthesized on a noble metal surface under ultrahigh vacuum conditions via a gas-mediated surface reaction protocol. Specifically, the controlled exposure to molecular oxygen efficiently deprotonates terminal alkyne moieties of 1,3,5-tris(4-ethynylphenyl)benzene (Ext-TEB) precursors adsorbed on Ag(111). At Tsub = 200 K, this O2-mediated reaction pathway features high chemoselectivity without poisoning the surface. Through mild annealing to 375 K, long-range ordered alkynyl-silver networks incorporating substrate atoms evolve, featuring Ag- bis-acetylide motifs, high structural quality and a regular arrangement of nanopores with a van der Waals cavity of ≈8.3 nm2.

New Organic Electrode Materials for Ultrafast Electrochemical Energy Storage.

Organic materials are both environmentally and economically attractive as potential electrode candidates. This Research News reports on a new class of stable and electrically conductive organic electrodes based on metal porphyrins with functional groups that are capable of electrochemical polymerization, rendering the materials promising for electrochemical applications. Their structural flexibility and the unique highly conjugated macrocyclic structure allows the produced organic electrodes to act as both cathode and anode materials giving access to fast charging as well as high cycling stability. The extreme thermal and chemical stability of the porphyrin-based organic electrodes and their chemical versatility suggest an important role for these molecular systems in the further development of novel electrochemical energy storage applications.

Observation of Cooperative Electronic Quantum Tunneling: Increasing Accessible Nuclear States in a Molecular Qudit.

As an extension of two-level quantum bits (qubits), multilevel systems, so-called qu dits, where d represents the Hilbert space dimension, have been predicted to reduce the number of iterations in quantum-computation algorithms. This has been tested in the well-known [TbPc2]0 single-molecule magnet (SMM), which allowed implementation of the Grover algorithm in a single molecular unit. In the quest for molecular systems possessing an increased number of accessible nuclear spin states, we explore herein a dimeric Tb2-SMM via single-crystal µ-SQUID measurements at sub-Kelvin temperatures. We observe ferromagnetic interactions between the TbIII ions and cooperative quantum tunneling of the electronic spins with spin ground state | J z = ±6⟩. Strong hyperfine coupling with the TbIII nuclear spins leads to a multitude of spin-reversal paths, leading to seven strong hyperfine-driven tunneling steps in the hysteresis loops. Our results show the possibility of reading out the TbIII nuclear spin states via cooperative tunneling of the electronic spins, making the dimeric Tb2-SMM an excellent nuclear spin qu dit candidate with d = 16.

The self-assembly and metal adatom coordination of a linear bis-tetrazole ligand on Ag(111).

We employ a linear linker molecule consisting of a benzene functionalised with two tetrazole moieties at para positions. Its self-assembly and coordination with the native silver adatoms and codeposited Fe adatoms on a Ag(111) surface under ultra high vacuum conditions are investigated by means of scanning tunnelling microscopy and X-ray photoelectron spectroscopy. We discover a rich spectrum of room-temperature stable Ag and Fe2+ coordination nodes depending on the formation temperature.