TY - JOUR A1 - Hickel, Tilmann A1 - Waske, Anja A1 - Tehranchi, Ali A1 - Bhattacharya, Biswajit A1 - Stawski, Tomasz M. A1 - Fellinger, Tim-Patrick A1 - Mehmood, Asad A1 - Witt, Julia A1 - Ozcan, Ozlem A1 - Guilherme Buzanich, Ana A1 - Kumar, Sourabh A1 - Mishra, Rajesh Kumar A1 - Holzer, Marco A1 - Stucchi de Camargo, Andrea Simone A1 - Agudo Jácome, Leonardo A1 - Manzoni, Anna A1 - Fantin, Andrea A1 - John, Elisabeth A1 - Hodoroaba, Vasile-Dan A1 - Bührig, Sophia A1 - Murugan, Jegatheesan A1 - Marschall, Niklas A1 - George, Janine A1 - Darvishi Kamachali, Reza A1 - Maaß, Robert A1 - Emmerling, Franziska T1 - Chemically complex materials enable sustainable high-performance materials N2 - Chemically complex materials (CCMats) 􀀀 including high-entropy alloys, oxides, and related multi-principal element systems 􀀀 offer a paradigm shift in materials design by leveraging chemical diversity to simultaneously optimize functional, structural, and sustainability criteria. The vastness of the compositional and structural space in CCMats propels the field into an expanding exploratory state. To reconcile functional and structural performance across this immense parameter space remains an open challenge. This Perspective evaluates the opportunities and challenges associated with harnessing chemical complexity across a broad spectrum of applications, such as hydrogen storage, ionic conductors, catalysis, magnetics, dielectrics, semiconductors, optical materials, and multifunctional structural systems. It is delineated how three central design strategies: targeted substitution (SUB), defect engineering (DEF), and diversity management (DIV) enable the reconciliation of high functional performance with long-term structural stability and environmental responsibility. Advances in computational thermodynamics, microstructure simulations, machine learning, and multimodal characterization are accelerating the exploration and optimization of CCMats, while robust data infrastructures and automated synthesis workflows are emerging as essential tools for navigating their complex compositional space. By fostering cross-disciplinary knowledge transfer and embracing data-driven design, CCMats are poised to deliver next-generation materials solutions that address urgent technological, energy, and environmental demands. KW - Chemically complex materials KW - Structural stability KW - Functional performance KW - Design strategies KW - Sustainability PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655598 UR - https://www.sciencedirect.com/science/article/pii/S1359028626000033?via%3Dihub DO - https://doi.org/10.1016/j.cossms.2026.101256 SN - 1359-0286 VL - 42 SP - 1 EP - 26 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-65559 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krause, Christina A1 - Szymoniak, Paulina A1 - Lohstroh, W. A1 - Juranyi, F. A1 - Zamponi, M. A1 - Frick, B. A1 - Al-Sabbagh, Dominik A1 - Emmerling, Franziska A1 - Zorn, R. A1 - Schönhals, Andreas T1 - Complex molecular dynamics of symmetric model discotic liquid crystals: Comparison of Hexakis(hepta-alkanoyloxy)triphenylene (HOT6) with Hexakis(hexa-alkyloxy)triphenylene (HAT6) N2 - This study investigates the complex molecular dynamics of discotic liquid crystals (DLCs) by comparing two structurally similar compounds: Hexakis(hepta-alkanoyloxy)triphenylene (HOT6) and Hexakis(hexa-alkyloxy)triphenylene (HAT6) having the same triphenyl core and the same length of the alkyl side chain. The difference of both materials is that the alkyl chain is linked by an oxygen bridge to the triphenylene core for HAT6 and by a ester group for HOT6. Using a combination of broadband dielectric spectroscopy, differential scanning calorimetry, X-ray scattering, and neutron scattering techniques, the research explores the glass transition phenomena and relaxation processes in these materials. HOT6, featuring ester linkages, exhibits distinct dynamic behavior compared to HAT6, including two separate glass transitions indicated by the 1- and 2-relaxation found by dielectric spectroscopy which are assigned to the glassy dynamics of the alkyl side chain in the intercolumnar space and that of the columns, respectively. The study reveals that the ester group in HOT6 leads to increased molecular rigidity and altered packing in the intercolumnar space, as evidenced by X-ray scattering and the vibrational density of states. Neutron scattering confirms localized methyl group rotations and a further relaxation process which relates to the -relaxation revealed by dielectric spectroscopy. The findings contribute to a deeper understanding of glassy dynamics in partially ordered systems and highlight the influence of molecular architecture on relaxation behavior in DLCs. KW - Discotic Liquid Crystals PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-655171 DO - https://doi.org/10.1039/d5sm01247c SN - 1744-6848 SP - 1 EP - 17 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65517 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pavlidis, Sotirios A1 - Fischer, Eric W. A1 - Opis-Basilio, Amanda A1 - Bera, Ayan A1 - Guilherme Buzanich, Ana A1 - Álvarez-Sánchez, María A1 - Wittek, Severin A1 - Emmerling, Franziska A1 - Ray, Kallol A1 - Roemelt, Michael A1 - Abbenseth, Josh T1 - Ambiphilic Reactivity and Switchable Methyl Transfer at a T-Shaped Bi(NNN) Complex Enabled by a Redox-Active Pincer Ligand N2 - We report the transition-metal-like reactivity of a geometrically constrained, ambiphilic bismuth(III) trisamide. Planarization of the Bi(III) center unlocks Bi−C bond formation when reacted with mild electrophiles (alkyl iodides and triflates) accompanied by two-electron oxidation of the utilized NNN pincer nligand. The preservation of the bismuth oxidation state is confirmed by single-crystal X-ray diffraction and X-ray absorption spectroscopy and corroborated by theoretical calculations. Sequential reduction of the oxidized ligand framework alters the reactivity of a generated Bi−Me unit, enabling controlled access to methyl cation, radical, and anion equivalents. The full [Bi(Me)(NNN)]+/•/− redox series was comprehensively characterized using NMR and EPR spectroscopy as well as spectro-electrochemistry. This work represents the first example of ligand-assisted, redox-neutral C−X bond splitting at bismuth, establishing a new paradigm for synthetic bismuth chemistry. KW - Pincer ligand KW - XAS KW - Redox PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-654948 DO - https://doi.org/10.1021/jacs.5c18955 SN - 0002-7863 VL - 148 IS - 2 SP - 2683 EP - 2692 PB - American Chemical Society (ACS) AN - OPUS4-65494 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gugin, Nikita A1 - Schwab, Alexander A1 - Carraro, Francesco A1 - Tavernaro, Isabella A1 - Falkenhagen, Jana A1 - Villajos, Jose A1 - Falcaro, Paolo A1 - Emmerling, Franziska T1 - ZIF-8-based biocomposites via reactive extrusion: towards industrial-scale manufacturing N2 - Mechanochemistry, a sustainable synthetic method that minimizes solvent use, has shown great promise in producing metal–organic framework (MOF)-based biocomposites through ball milling. While ball milling offers fast reaction times, biocompatible conditions, and access to previously unattainable biocomposites, it is a batch-type process typically limited to gram-scale production, which is insufficient to meet commercial capacity. We introduce a scalable approach for the continuous solid-state production of MOF-based biocomposites. Our study commences with model batch reactions to examine the encapsulation of various biomolecules into Zeolitic Imidazolate Framework-8 (ZIF-8) via hand mixing, establishing a foundation for upscaling. Subsequently, the process is scaled up using reactive extrusion, enabling continuous and reproducible kilogram-scale production of bovine serum albumin (BSA)@ZIF-8 with tunable protein loading. Furthermore, we achieve the one-step formation of shaped ZIF-8 extrudates encapsulating clinical therapeutic hyaluronic acid (HA). Upon release of HA from the composite, the molecular weight of HA is preserved, highlighting the industrial potential of reactive extrusion for the cost-effective and reliable manufacturing of biocomposites for drug-delivery applications. KW - Mechanochemistry KW - Extrusion KW - Biocompoites KW - MOFs PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-654777 DO - https://doi.org/10.1039/D5TA08276E SN - 2050-7496 SP - 1 EP - 14 PB - Royal Society of Chemistry AN - OPUS4-65477 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Adhami, Forogh A1 - Safavi, Maliheh A1 - Ehsani, Maryam A1 - Ardestani, Sussan K. A1 - Emmerling, Franziska A1 - Simyari, Farzaneh T1 - Synthesis, crystal structure, and cytotoxic activity of novel cyclic systems in [1,2,4]thiadiazolo[2,3-a]pyridine benzamide derivatives and their copper(ii) complexes N2 - Three N-(pyridine-2-ylcarbamothioyl)benzamide derivatives were synthesized by the reaction of potassium thiocyanate, benzoyl chloride, and 2-amino pyridine derivatives in one pot. The obtained derivatives were oxidized using copper(II) chloride. During the oxidation, two hydrogen atoms were removed, cyclization of the derivatives occurred, and finally, three new N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives were produced. Coordination of these three new derivative ligands to the copper(II) ion resulted in the formation of three new complexes: dichlorobis(N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide)copper(II), dichlorobis(N-(7-methyl-2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2ylidene)benzamide)copper(II), and dichlorobis(N-(5-methyl-2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide)copper(II). All the synthesized products were characterized by IR, 1H NMR, and 13C NMR spectroscopies. Crystal structures of the obtained N-(pyridine-2-ylcarbamothioyl)benzamide derivatives, N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives, and complexes were determined using X-ray single-crystal diffraction; the positions of atoms, bond lengths, bond angles, and dihedral angles were also determined. In all complexes, the coordination of two large monodentate ligands and two chloride anions to the copper(II) ion resulted in the formation of a stable planar geometry around the central ion. Three N-(pyridine-2-ylcarbamothioyl)benzamide derivatives, three N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives, and three complexes were evaluated for their cytotoxicity against five human cancer cell lines (breast cancer cell line MDA-MB-231, neuroblastoma cell line SK-N-MC, prostate adenocarcinoma cell line LNCap, nasopharyngeal epidermoid carcinoma cell line KB, and liver cancer cell line HEPG-2) using an in vitro analysis. The N-(pyridine-2-ylcarbamothioyl)benzamide derivatives showed no cytotoxic activity, whereas the N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives and their complexes showed significant cytotoxicity, especially against MDA-MB-231 and LNCap cell lines. The complexes demonstrated smaller IC50 values than N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide derivatives. KW - Copper complexes PY - 2014 DO - https://doi.org/10.1039/c3dt52905c SN - 1477-9226 VL - 43 IS - 21 SP - 7945 EP - 7957 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65449 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stolar, Tomislav A1 - Bayram, Dilara A1 - May, Anastasia A1 - Sundermann, Remie A1 - Prinz, Carsten A1 - Meyer, Klas A1 - Myxa, Anett A1 - Falkenhagen, Jana A1 - Emmerling, Franziska T1 - Selective mechanochemical conversion of post-consumer polyethylene terephthalate waste into hcp and fcu UiO-66 metal–organic frameworks N2 - Single-use plastics strongly contribute to plastic pollution, and less than 10% of plastic waste is recycled globally. Here, we present a selective mechanochemical protocol for converting post-consumer polyethylene terephthalate (PET) transparent bottles and coloured textile waste into the porous metal–organic framework (MOF) UiO-66 materials. We used time-resolved in situ (TRIS) synchrotron powder X-ray diffraction and Raman spectroscopy to monitor the depolymerization of PET during ball milling. To convert disodium terephthalate to UiO-66, we developed base and base-free synthetic routes that lead to fcu and hcp UiO-66 phases, respectively, including the first ever synthesis of hcp UiO-66 by mechanochemistry. Our results demonstrate the potential of mechanochemistry to selectively access fcu and hcp UiO-66 phases using post-consumer PET waste. KW - Mechanochemistry PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653958 DO - https://doi.org/10.1039/D4MR00126E SN - 2976-8683 SP - 1 EP - 8 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65395 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stolar, Tomislav A1 - Alić, Jasna A1 - Casali, Lucia A1 - Gugin, Nikita A1 - Baláž, Matej A1 - Michalchuk, Adam A1 - Emmerling, Franziska ED - Stolar, Tomislav T1 - Mechanochemistry: Looking back and ahead N2 - Starting with the discovery of fire and the preparation of food in prehistoric times, mechanochemistry is the oldest form of chemistry that humans have controlled. Mechanochemical practices, such as grinding with a mortar and pestle, continued into the Middle Ages until dedicated scientific studies began in the 19th century. Since then,research in mechanochemistry has shown that many chemicalreactions can be performed via mechanical force without or with small amounts of solvent. Besides being time, material, and energy efficient, mechanochemical reactions often yield products that differ from those obtained in solution. Therefore, not only is mechanochemistry greener and more sustainable than conventional solution chemistry, but it also has the added value of providing new reactivity and selectivity. This is especially important today, when chemists need to invent high-performance materials, intermediates, and products with the use of sustainable feedstocks and develop environmental remediation pathways. At the same time, time-resolved in situ monitoring and computational modeling are necessary for addressing fundamental questions about the atomistic, molecular, and electronic nature of mechanochemical reactivity. Integrating digitalization, robotics, and artificial intelligence tools promises to increase the reproducibility and scalability of mechanochemical processes. Further evolution of mechanochemistry is expected to have a transformative effect on the chemical industry. KW - Mechanochemistry PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653962 DO - https://doi.org/10.1016/j.chempr.2025.102880 SN - 2451-9294 VL - 12 IS - 2 SP - 1 EP - 27 PB - Elsevier BV AN - OPUS4-65396 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chakraborty, Gouri A1 - Das, Prasenjit A1 - Bhattacharya, Biswajit A1 - Prinz, Carsten A1 - Emmerling, Franziska A1 - Thomas, Arne T1 - Room-temperature superprotonic conductivity in COOH-functionalized multicomponent covalent organic frameworks N2 - In solid materials, the development of hydrogen bonding (H-bonding) networks within pores is crucial for efficient proton conductance. In this study, a chemically stable carboxylic acid-functionalized, quinoline-linked 2D microporous covalent organic framework (COF) (Qy-COOH) was synthesized using the Doebner multicomponent reaction (MCR) and compared to a similar framework lacking the –COOH functionality (Qy-H), prepared via an MC Domino reaction. The proton conductivity of the –COOH-functionalized MCR-COF was significantly enhanced, reaching 10−2 S cm−1, attributed to strong H-bonding interactions between water molecules and the dangling –COOH groups within the COF pores. In contrast, the analogous Qy-H framework exhibited a much lower proton conductivity of 10−5 S cm−1, while an imine-based COF showed only 10−6 S cm−1. This work represents the first demonstration of a general strategy to achieve efficient proton conduction in a class of layered 2D –COOH-functionalized COFs, offering superprotonic conductivity without requiring additives at room temperature. The MCR-COF design approach provides a promising pathway for developing highly stable and high-performance proton-conducting materials. KW - Multicomponebt KW - COF KW - Proton Conductivity KW - Superprotonic PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653526 DO - https://doi.org/10.1039/D5SC06953J SN - 2041-6520 SP - 1 EP - 9 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65352 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmalz, Alina A1 - Eby, Charles Gaston A1 - Moss, Caitlin A1 - Bhattacharya, Biswajit A1 - Emmerling, Franziska T1 - Thermally Robust 1D Cu(I) Phosphonate Coordination Polymer Exhibiting Enhanced Proton Conductivity via Humidity‐Driven Pathways N2 - The development of thermally stable solid-state proton conductors (SSPCs) is crucial for advancing energy-conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this work, we report the solvothermal synthesis and characterization of a novel, 1D Cu(I) coordination polymer, {Cu(ADP)0.5(BPY)}n (BAM-5), based on anthracenediylphosphonate (H2ADP) and 4,40 -bipyridine (BPY). Single-crystal X-ray diffraction revealed that BAM-5 crystallizes in the triclinic space group P1 and shows a 1D ladder structure connected by the H2ADP and organic BPY linkers, which is assembled into a 2D layer via O−H···O hydrogen bonding interactions between uncoordinated oxygen and the O−H of the phosphonate group. Thermogravimetric and dynamic water sorption analysis demonstrated exceptional thermal robustness of BAM-5 until 230°C and notable water affinity. Proton conductivity measurements found increasing proton conductive properties with increasing temperature and relative humidity.The latter is correlated with the material’s water uptake since the structure itself does not contain any permanent lattice water molecules. A maximum proton conductivity of 6.6 × 10−6 S cm−1 was found at 80°C and 98% RH. To the best of our knowledge, no dense, nonporous 1D coordination polymer without lattice or coordinated solvent molecules has shown comparable proton con� ductivity. The high activation energy suggests a combination of both, a Grotthuss-type proton hopping through the hydrogen� bonded framework, and a vehicular process, in which protons are carried along with absorbed water molecules. KW - Coordination polymers KW - Phosphonate ligand KW - Proton conduction KW - X-ray diffraction PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-651382 DO - https://doi.org/10.1002/zaac.202500187 SN - 0044-2313 SP - 1 EP - 8 PB - Wiley VHC-Verlag AN - OPUS4-65138 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - INPR A1 - Morcillo, Dalia A1 - Oelze, Marcus A1 - Seena Prem, Pranav A1 - de Oliveira Guilherme Buzanich, Ana A1 - Emmerling, Franziska A1 - Recknagel, Sebastian A1 - Panne, Ulrich A1 - Abad Andrade, Carlos Enrique T1 - Lithium isotope fractionation as an early indicator of degradation mechanisms in lithium-ion batteries N2 - Aging in lithium-ion batteries (LIBs) degrades performance and hinders sustainability, demanding advanced diagnostics for early failure prediction. We investigate lithium isotope fractionation (LIF) as an innovative probe of degradation in lithium cobalt oxide (LCO) coin cells aged over 0−700 cycles. High-precision multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) quantified δ7Li variations across cell stages: non-cycled (0 cycles), newly formed (5 cycles), semi-aged (250 cycles), and fully aged (700 cycles). During early cycling (≤ 45 cycles), chemical processes drive 7Li enrichment at the anode (δ7Li vs LSVEC = +12 ‰) through solid electrolyte interphase (SEI) formation, while the cathode depletes in 7Li (δ7Li vs LSVEC = −0.7 ‰). Beyond 45 cycles, electric field-induced migration predominates, promoting 6Li intercalation into the anode and increasing the δ7Li of the cathode by 8.1 ‰. Mass balance verifies isotope conservation, attributing shifts to redistribution and trapping. Complementary electrochemical impedance spectroscopy (EIS) and X-ray absorption spectroscopy and diffraction confirm SEI expansion, cobalt oxidation, lattice shrinkage, and changes in electrode structure, corroborating LIF trends. Notably, a δ7Li inflection at approximately 270 cycles anticipates end-of-life by 70 cycles, surpassing traditional methods in sensitivity. LIF emerges as a predictive indicator of aging mechanisms, informing optimized designs for durable LIBs. KW - Lithium isotope fractionation KW - Lithium-ion batteries KW - Degradation mechanisms KW - LiCoO2 cathodes KW - LCO KW - Isotopic tracing KW - Lithium isotopes PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-650945 DO - https://doi.org/10.26434/chemrxiv-2025-16lvq SP - 1 EP - 19 AN - OPUS4-65094 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -