Solid State Research Articles

Evolution of Peptidomimetics-Based Chiral Assemblies of β-Sheet, α-Helix, and Double Helix Involving Chalcogen Bonds.

Developing chiral assemblies that mimic biological secondary structures, e.g., protein β-sheet, α-helix, and DNA double helix, is a captivating goal in supramolecular chemistry. Here, we create a family of biomimetic chiral assemblies from alanine-based peptidomimetics, wherein the incorporation of N-terminal 2,1,3-benzoselenadiazole groups enables the rarely utilized chalcogen bonding as the adhesive interaction. While the alanine-based acylhydrazine molecule 1L was designed as a building unit with an extended conformation, simple derivatization of 1L affords folded unilateral N-amidothiourea 2L with one β-turn and bilateral N-amidothiourea 3L with two β-turns. This derivatization leads to the evolution of molecular assemblies from β-sheet organization (1L) to single helix (α-helix mimic, 2L) and ultimately to double helix (3L), illustrating an evolutionary route relating the structures and superstructures. In the case of the double helix formed by 3L, an unexpected cis-form that brings the two β-turns into one side was observed, stabilized via the π···π interaction between two N-terminal 2,1,3-benzoselenadiazole groups. This conformation allows double-crossed N-Se···S═C chalcogen bonds to support a DNA-like P-double helix featuring intrastrand noncovalent interactions and interstrand covalent linkages, surviving in both the solid state and in dilute acetonitrile solution phase.

Reactivity of Strontium Hydride Supported by the Superbulky Hydrotris(pyrazolyl)borate Ligand.

Hydrogenolysis of [(TpAd,iPr)Sr{CH(SiMe3)2}] (1) (TpAd,iPr = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate) in hexane solution under 20 atm of H2 allowed for the isolation of strontium hydride [(TpAd,iPr)Sr(μ-H)]2 (2) in good yield. Complex 2 exhibits the dimeric nature in solid state, featuring two different bond modes between the Sr center and TpAd,iPr ligand. Treatment of complex 2 with PhC(H)═NtBu or PhCH2Bpin (Bpin = pinacolateborane) afforded the strontium amide complex [(TpAd,iPr)Sr{N(CH2Ph)(tBu)}] (4) and hydroborate complex [(TpAd,iPr)Sr{μ-HBpin(CH2Ph)}] (5), respectively. Reactions of complex 2 with 2-picoline, 2-phenylquinoline, or 2-phenylpyridine led to the formation of strontium 2-pyridylmethylene/2-picoline complex [(TpAd,iPr)Sr(2-CH2-Py)(2-picoline)] (6), reductively coupling diphenyl-biquinolide complex [{(TpAd,iPr)Sr}2(2,2'-Ph2-4,4'-dihydro-4,4'-biquinolide)] (7), and diphenyl-bipyridyl radical complex [(TpAd,iPr)Sr(6,6'-Ph2-2,2'-bipyridyl)] (8), separately. All of the complexes have been well characterized, including NMR spectrum and single-crystal X-ray analysis.

Ternary π-π Stacking Complexes by Allosteric Regulation in Multilayer Nanographenes.

Construction of π-π stacking supramolecular complexes with more than two different components is challenging due to the weak and directionless nature of dispersion interactions. Here, we report ternary complexes of a ditopic nanographene tetraimide (1), α-substituted phthalocyanine (Pc), and polyaromatic hydrocarbons (PAHs) in solution and the crystalline state via allosteric regulation. Binding of one Pc gives rise to significant distortion and conformational changes in 1 that in turn lead to the inhibition of the second binding of Pc. The conformational changes associated with first binding allowed an allosteric binding of a third component (PAHs) to form ternary complexes in solution. 1H NMR titration revealed moderately high thermodynamic stability for the ternary complexes in CDCl3. Competition between allosterically regulated ternary complexes ([Pc·1·PAH]) and 1:2 stoichiometric binary complexes of 1 with PAHs ([PAH·1·PAH]) was elucidated. Further, the selective formation of ternary complexes in solution led to the generation of ternary cocrystals from a 1:1:1 mixture of three components in solution. Our work shows that large π-conjugated nanographenes designed with allosteric recognition sites allow the construction of multilayer ternary complexes in solution and the solid state even with dispersive π-π interactions.

Where Fluoride Is Present, Hexafluorosilicate Might Be Encountered: Supramolecular Binding of the SiF6 2- Anion by Nanojars.

While the fact that HF etches glass is rather common chemical knowledge, the reaction of fluoride ions in an organic solvent with glassware under alkaline conditions has not yet been documented. It becomes apparent that, in general, whenever any fluorine-containing material is handled in silicon-based glassware, the possible presence of SiF6 2- should be considered regardless of the pH of the reaction medium. Subsequent to the initial, inadvertent synthesis by the reaction of CuF2 with laboratory glassware, hexafluorosilicate-entrapping supramolecular assemblies (nanojars) of the formula [SiF6⊂{cis-CuII(μ-OH)(μ-pz)} n ]2- (Cu n SiF 6 ; n = 28, 30, 32, 34) were rationally prepared by the reaction of Cu2+ with pyrazole (Hpz) in the presence of a base and SiF6 2- ions or by combining Cu n CO 3 with H2SiF6 or HF. This work demonstrates that nanojars are excellent anion-binding agents not only for trigonal planar/pyramidal or tetrahedral anions but also for larger, octahedral anions, which are bound exclusively by charge-assisted hydrogen bonds. The SiF6 2- anion guest is preferentially bound by a larger Cu32 host, whereas CO3 2- favors a smaller Cu27 nanojar. The Cu n SiF 6 mixture was characterized by electrospray ionization mass spectrometry as well as variable-temperature, paramagnetic 1H and 19F NMR spectroscopy in solution, complemented by single-crystal X-ray diffraction studies in the solid state, which reveal the unprecedented structure of a Cu8+14+10 nanojar (where Cu8, Cu10, and Cu14 are the component Cu x metallamacrocycles of the Cu32 nanojar).

Structural, optical, and thermal traits of Sm³⁺-doped SrB₂O₄ phosphors for solid-state lighting applications

We synthesized Sm³⁺-doped SrB₂O₄ phosphors through a solid-state reaction method, varying the Sm³⁺ doping concentrations. Structural and morphological characteristics of material were investigated using Fourier-transform infrared spectroscopy (FTIR), X-Ray Diffraction (XRD) and scanning electron microscopy (SEM). Optical transitions were analyzed by recording the diffuse reflectance spectroscopy, while photoluminescent (PL) spectra were used to evaluate luminescence properties. The PL spectra revealed a strong orange emission at 598 nm under 402 nm excitation. The optimal Sm³⁺ doping concentration was determined to be 0.02 mol, beyond which concentration quenching occurred. This quenching is attributed to exchange-type interactions, which facilitate non-radiative energy relaxation. The CIE color chromaticity coordinates of all the synthesized phosphors fell within the orange region of the chromaticity diagram. Temperature dependent photoluminescence revealed lower activation energy and phonon energy. Thermal quenching temperature was calculated which is inline with commercially available LEDs. All of these results indicate the candidature of SrB2O4 phosphor doped with Sm3+ ions for solid state lighting and optical thermal sensing applications.

Organic Cationic-Coordinated Perfluoropolymer Electrolytes with Strong Li+-Solvent Interaction for Solid State Li-Metal Batteries.

The practical application of solid-state polymer lithium-metal batteries (LMBs) is plagued by the inferior ionic conductivity of the applied polymer electrolytes (PEs), which is caused by the coupling of ion transport with the motion of polymer segments. Here, solvated molecules based on ionic liquid and lithium salt with strong Li+-solvent interaction are inserted into an elaborately engineered perfluoropolymer electrolyte via ionic dipole interaction, extensively facilitating Li+ transport and improving mechanical properties. The intensified formation of solvation structures of contact ion pairs and ionic aggregates, as well as the strong electron-withdrawal properties of the F atoms in perfluoropolymers, give the PE high electrochemical stability and excellent interfacial stability. As a result, Li||Li symmetric cells demonstrate a lifetime of 2500 h and an exceptionally high critical current density above 2.3 mA cm-2, Li||LiFePO4 batteries exhibit consistent cycling for 550 cycles at 10 C, and Li||uncoated LiNi0.8Co0.1Mn0.1O2 cells achieve 1000 cycles at 0.5 C with an average Coulombic efficiency of 98.45 %, one of the best results reported to date based on PEs. Our discovery sheds fresh light on the targeted synergistic regulation of the electro-chemo-mechanical properties of PEs to extend the cycle life of LMBs.

Photomanipulatable colloidal clusters from the aggregation of azo molecular glass spheres.

Colloidal clusters with well-controlled shapes have attracted extensive interest in the fields of materials, chemistry, physics, and biology. This communication reports the controllable fabrication of photoresponsive colloidal clusters with a wide range of adjustable sizes and complex architectures through an approach of microsphere formation and fusion. The clusters of colloidal spheres were obtained via adding ethanol dropwise into a tetrahydrofuran solution of an isosorbide-based azo compound (IAC-4). In the process, the colloidal spheres with soft and sticky shells were first formed in the dispersion. After stirring at an appropriate rate and time, clusters composed of controlled numbers of colloidal spheres were obtained. With increasing stirring time, the colloidal spheres in the clusters underwent fusion transforming into a range of structures with particular architectures. The structure formation, evolution and control were investigated by scanning electron microscopy (SEM) and dynamic light scattering (DLS). Under linearly polarized light irradiation, colloidal spheres in the clusters in the solid state were observed to be stretched along the direction of electric-field oscillation and these clusters were thus transformed into complex particles with unique morphologies. This exploration can lead to a new methodology to effectively fabricate colloidal clusters with complex architectures and shed new light on colloidal packing and organization under the driving forces of extrinsic energy input.

Flexible Coordination of SacNac Ligands in Iridium Complexes and their Application to Catalytic Hydroboration

AbstractHerein, we report the synthesis and characterization of a small family of Ir(I) and Ir(III) complexes supported by β‐thioketoiminates (SacNac) ligands. All complexes were fully characterized by IR, 1D and 2D NMR, and Elemental Analysis (e.a.) experiments. X‐ray diffraction studies were carried out to corroborate the structure of compounds [Ir(cod)(SacNac)] (1) (cod=1,5‐cyclooctadiene), [Ir(dmb)(SacNac)] (2) (dmb=2,3‐dimethyl‐1,3‐butadiene) and [IrCp*(SacNac‐H)(Cl)2] (8) (Cp*=pentamethyl‐cyclopentadienyl). Complexes 1 and 2 are Ir(I) species and have square‐planar geometry in solid state, with bond angles and distances that suggest semi‐aromaticity in the six‐membered ring. To the best of our knowledge, we report the first mono‐coordination mode of a SacNac ligand via sulfur atom in complex 8. Also, we report the first application of iridium‐SacNac complexes as catalytic precursors in hydroboration reactions, where Ir(III) species give the best results.

A Melt-Processable Metal Halide Perovskite Ferroelectric.

Molecular ferroelectrics have increasingly garnered significant attention in both fundamental scientific research and technological applications due to their ease of processing, lightweight nature, and mechanical flexibility. Among these, metal halide perovskite ferroelectrics (MHP FEs), a subset of molecule-based ferroelectrics, exhibit diverse functionalities owing to their distinctive structures, thus emerging as a focal point of molecular ferroelectrics research. However, thin films, the predominant application form for MHP FEs, primarily rely on spin-coating, which presents considerable limitations. The development of melt-processable MHP FEs has been sparse, largely due to the challenge of integrating ferroelectricity with meltability. In this context, we propose a rational strategy for the successful synthesis of a melt-processable MHP FE, (MBPA)2PbBr4 (MBPA = N-methyl bromopropylammonium), featuring a notably low congruent melting temperature and excellent molten stability. The reversibility of solid and liquid states was demonstrated by X-ray diffraction and Raman and IR spectrum. Scanning electron microscopy examinations show a better quality of the melt-processed thin films compared to spin-coated ones. This study marks the successful implementation of integrating ferroelectricity and melt-processability into melt-processable MHP FEs, paving the way for a novel approach in processing MHP FEs and facilitating their future applications.

Characterization and Optimization of the Photoluminescent Properties of Imidazo[1,5‐a]quinolines

AbstractIn our previous work we could show, that Imidazo[1,5‐a]quinolines are compounds with interesting optical properties. In this work, we optimized the photoluminescent properties of imidazo[1,5‐a]quinolines by following outlined trends in our previous work. By introducing electron‐rich and electron‐poor residual groups on the imidazole ring, the quantum yield (QY) could be significantly increased. This indicated a clear advantageous substitution pattern for this system. In addition, cyclic voltammetric and UV/vis measurements in solid state lay the foundation for applications, such as organic light‐emitting diodes (OLEDs).

Photo‐Induced Ultrafast Charge Transfer and Air‐Stable Radical Formation in Tetraphenylpyrene Derivatives

AbstractStable organic radicals generated by photo‐excitation hold applications in molecular switching devices and information storage. It remains challenging to develop photo‐generated radical materials with rapid response and air stability in the solid state. Here, we report a structure based on 1,3,6,8‐tetraphenylpyrene derivative (Py‐TTAc) displaying photo‐induced radicals with air stability in the solid state. Photo‐induced electron transfer, exposed to a 365 nm ultraviolet lamp for 1 minute, affords radicals in Py‐TTAc powder as confirmed by electron paramagnetic resonance (EPR) spectroscopy. The maximum radical concentration reaches 2.21 % after continuous irradiation for 1 hour and recurs more than 10 times without any chemical degradation. The mechanistic study according to the femtosecond transient absorption (fsTA) and X‐ray technology suggests that the radicals are derived from photo‐induced symmetry‐breaking charge separation (SB‐CS) and stabilized through non‐covalent interactions. The photo‐generated stable radical system is employed in anti‐counterfeiting paper and optoelectronic device applications. This study will provide insights into the development of photoactive organic radical materials.

Photo-Induced Ultrafast Charge Transfer and Air-Stable Radical Formation in Tetraphenylpyrene Derivatives.

Stable organic radicals generated by photo-excitation hold applications in molecular switching devices and information storage. It remains challenging to develop photo-generated radical materials with rapid response and air stability in the solid state. Here, we report a structure based on 1,3,6,8-tetraphenylpyrene derivative (Py-TTAc) displaying photo-induced radicals with air stability in the solid state. Photo-induced electron transfer, exposed to a 365 nm ultraviolet lamp for 1 minute, affords radicals in Py-TTAc powder as confirmed by electron paramagnetic resonance (EPR) spectroscopy. The maximum radical concentration reaches 2.21 % after continuous irradiation for 1 hour and recurs more than 10 times without any chemical degradation. The mechanistic study according to the femtosecond transient absorption (fsTA) and X-ray technology suggests that the radicals are derived from photo-induced symmetry-breaking charge separation (SB-CS) and stabilized through non-covalent interactions. The photo-generated stable radical system is employed in anti-counterfeiting paper and optoelectronic device applications. This study will provide insights into the development of photoactive organic radical materials.

Deciphering the Conformations of Glutathione Oxidized Peptide: A Comparative NMR Study in Solution and Solid-State Environments.

Glutathione (GSH) and its oxidized dimer (GSSG) play an important role in living systems as an antioxidant, balancing the presence of reactive oxygen species (ROS). The central thiol (-S-S-) bond in GSSG can undergo free rotation, providing multiple conformations with respect to the S-S bridge. The six titratable sites of GSSG, which are influenced by pH variations, affect these conformations in solution, whereas in solids, additionally crystal packing effects come into play. In view of differing reports about the structure of GSSG in literature, we have here conducted an extensive reexamination of its conformations using NMR, and contrasting results have been obtained for solution and solid state. In solution, the existence of more than one antiparallel orientation of the monomer unit with different hydrogen bonding schemes has been indicated by NOE and amide temperature coefficient results. On the other hand, in the solid-state, a 1H-1H double-quantum (DQ) to 13C single-quantum (SQ) correlation study has confirmed a parallel orientation, consistent with the reported X-ray crystal structure. Experimentally assigned solid-state NMR resonances have been validated using GIPAW calculations incorporated in the Quantum ESPRESSO package.

Columnar Organization of Nonalternant Fluorinated Dehydrobenzannulenes.

Two new partially fluorinated dehydrobenzannulenes have been prepared by inter- and intramolecular oxidative homocoupling of diyne precursors. These systems contain fluorinated and nonfluorinated arene rings in a desymmetrized non-alternant arrangement. Both macrocycles are roughly planar and organize into extended columns in the solid state. The assembly of these columns is mediated by the combination of dispersion interactions, slipped [π⋅⋅⋅π] stacking interactions of the perfluorinated rings with each other, and their association with the nonfluorinated rings in the molecules of the neighboring macrocycles. These results suggest that partial fluorination of dehydrobenzannulenes can serve as a versatile motif for their assembly into columnar superstructures.

Benzo-Fused BOPAM Fluorophores: Synthesis, Post-functionalization, Photophysical Properties and Acid sensing Applications.

A novel category of asymmetric boron chromophores with the attachment of two BF2 moieties denoted as BOPAM has been successfully synthesized via a one-pot three-step reaction starting from N-phenylbenzothioamide. This synthetic route results in the production of [a] and [b]benzo-fused BOPAMs along with post-functionalization of the [a]benzo-fused BOPAMs. The photophysical properties of these compounds have been systematically investigated through steady-state absorption and fluorescence emission measurements in solvents at both ambient and cryogenic temperatures, as well as in the solid state. Computational methods have been employed to elucidate the emissive characteristics of the benzo-fused BOPAMs, revealing distinctive photophysical attributes, including solvent-dependent fluorescence intensity. Remarkably, certain BOPAM derivatives exhibit noteworthy photophysical phenomena, such as the induction of off-on fluorescence emission under specific solvent conditions and the manifestation of intermolecular charge transfer states in solid-state matrices. Through post-functionalization strategies involving the introduction of electron-donating groups onto the [a]benzo-fused BOPAM scaffold, an intramolecular charge transfer (ICT) pathway is activated, leading to substantial fluorescence quenching via non-radiative decay processes. Notably, one [a]benzo-fused BOPAM variant exhibits a pronounced fluorescence enhancement upon exposure to acidic conditions, thereby underscoring its potential utility in pH-sensing applications.

Toughening Immiscible Polymer Blends: The Role of Interface-Crystallization-Induced Compatibilization Explored Through Nanoscale Visualization.

This study explores the novel approach of interface-crystallization-induced compatibilization (ICIC) via stereocomplexation as a promising method to improve the interfacial strength in thermodynamically immiscible polymers. Herein, two distinct reactive interfacial compatibilizers, poly(styrene-co-glycidyl methacrylate)-graft-poly(l-lactic acid) (SAL) and poly(styrene-co-glycidyl methacrylate)-graft-poly(d-lactic acid) (SAD) are synthesized via reactive melt blending in an integrated grafting and blending process. This approach is demonstrated to enhance the interfacial strength of immiscible polyvinylidene fluoride/poly l-lactic acid (PVDF/PLLA) 50/50 blends via ICIC. IR nanoimaging indicates a cocontinuous morphology in the blends. The blend compatibilized with SAD exhibits a higher storage modulus, as unveiled by small amplitude oscillatory shear (SAOS) in the melt state at a temperature below the melting temperature of the stereocomplex (SC) crystals and by DMTA measurements in the solid state. This increase is attributed to the formation of a 200-300 nm thick rigid interfacial SC crystalline layer that is directly visible using AFM imaging and chemically characterized via IR nanospectroscopy. This ICIC also results in a significant toughening of the blend, with the elongation at break increasing more than 20-fold. Moreover, the fracture toughness factor obtained from single edge-notch bending (SENB) tests is doubled with ICIC as compared to the uncompatibilized blend, indicating the strong crack-resistance capability as a result of ICIC. This improvement is also evident in SEM images, where thinner and longer fibrillation is observed on the fractured surface in the presence of ICIC.

Putting the squeeze on valence tautomerism in cobalt-dioxolene complexes

Molecules that can reversibly switch between electronic states under an external stimulus are of interest to numerous applications. Complexes of open shell metal ions with redox active ligands undergo valence tautomerism, resulting in magnetic, colour and structural switching, relevant to data storage and actuators. However, the precise structural changes occurring during valence tautomerism in the solid state are unclear due to the lack of atomic-resolution characterization. Here, variable temperature and high-pressure single crystal X-ray diffraction is used to characterize valence tautomerism in two isostructural cobalt complexes, [Co(bis(6-methyl-2-pyridylmethyl) amine)(3,5-di-tert-butyl-1,2-dioxolene)]+ and [Co(tris(6-methyl-2-pyridylmethyl)amine)(3,5-di-tert-butyl-1,2-dioxolene)]+ to atomic resolution. The less sterically hindered dimethylated complex exhibits two-step thermally-induced interconversion between the high-spin CoII-seminquinonate and low-spin CoIII-catecholate forms (valence tautomerism) at 155 and 95 K due to the presence of two symmetry-independent complexes. In contrast, the more sterically hindered trimethylated complex does not display thermal valence tautomerism. Both complexes exhibit unique behaviour under high pressure. The dimethylated species undergoes gradual, one-step valence tautomerism in both symmetry-independent complexes concurrently between 0.43 GPa and 1.30 GPa. In the trimethylated species, pressure is sufficient to overcome steric hindrance, leading to one-step valence tautomerism between 2.60 GPa and 3.10 GPa, demonstrating pressure-triggered valence tautomerism in a thermally inactive complex. This study is among the few investigations using in situ high-pressure single crystal X-ray diffraction to achieve atomic-level structural characterization of valence tautomerism, aiding the development of robust structure-property relationships in these types of complexes.

TICT, and Deep-Blue Electroluminescence from Acceptor-Donor-Acceptor Molecules.

Donor-acceptor (D-A) materials based on butterfly-shaped molecules could inhibit exciton-migration-induced quenching due to molecular twist. To explore this attribute towards beneficial photophysical properties, three novel bipolar acceptor-donor-acceptor (A-D-A) molecules with triphenyl triazine end capping along with substitution ortho to the Tröger's base (TB) scaffold varying from H, Me, and F were explored. The installation of H/Me/F imparted an electron push-pull effect with concomitant maneuvering of photophysical properties. On increasing solvent polarity, a remarkable bathochromic shift with a significant decrease in emission efficiency was observed due to the twisted intramolecular charge transfer state (TICT). Emission enhancement in the ethylene glycol-water mixture and diminution in the THF-water mixture further confirmed the existence of TICT states in these TBs. The torsional dynamics in the excited state were also evidenced by the time-dependent density-functional theory (TD-DFT) calculations. Owing to the butterfly architecture of the TB that suppressed TICT, TB-Trzs exhibited a significant blue shift, accompanied by a favorable quantum yield in the solid state. Among the three compounds, Me-TB-Trz exhibited deep-blue photoluminescence and was explored as a dopant in organic light-emitting diodes (OLEDs) to obtain deep-blue electroluminescence of brightness 4128 cdm-2 and CIE coordinates of (0.16, 0.09).

Room‐Temperature Phosphorescence of Cocrystals of Aromatic Bisimides and Triplet Sensitizer Pt(acac)2

AbstractFour sterically shielded aromatic bisimides are synthesized and their ability to form cocrystals with the triplet sensitizer platinum(II) acetylacetonate (Pt(acac)2) is investigated. Single crystals of the individual electron‐deficient bisimides are studied first, two showing bright blue fluorescence with quantum yields of up to 28%, while the other two barely emit at all. After successful cocrystallization of all four aromatic bisimides with the electron‐rich Pt(II) complex, two different stoichiometries, either 1:1 or 1:2, are found in the crystalline solid state, whose absorbance and photoluminescence exhibit distinct bathochromic shifts. While two naphthalene bisimides show strong and long‐lived room‐temperature phosphorescence (RTP) with quantum yield exceeding 50%, the other two aromatic bisimides show only minor photoluminescence at RT, but a bright low‐temperature phosphorescence (LTP) at 80 K. Theoretical calculations reveal the importance of changing the magnetic quantum number ml of the involved d‐orbitals at the platinum center as well as the alignment of the Pt(II) center above an aromatic C─C bond for an efficient intersystem crossing in these hybrid systems.

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper-Gold System.

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core-shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder-order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al2O3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. This research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.