Heteromeric Completive Self-Sorting in Coordination Cage Systems.

Heteroleptic coordination cages, nonstatistically assembled from a set of matching ligands, can be obtained by mixing individual components or via cage-to-cage transformations from homoleptic precursors. Based on the latter approach, we here describe a new level of self-sorting in coordination cage systems, namely, 'heteromeric completive self-sorting'. Here, two heteroleptic assemblies of type Pd2A2B2 and Pd2A2C2, sharing one common ligand component A but differing in the other, are shown to coexist in solution. This level of self-sorting can be reached either from a statistical mixture of assemblies based on some ligands B and C or, alternatively, following a first step of integrative self-sorting giving a distinct Pd2B2C2 intermediate. While subtle enthalpic factors dictate the outcome of the self-sorting, we found that it is controllable. From a unique set of three ligands, we demonstrate the transition from strict integrative self-sorting forming a Pd2AB2C cage to heteromeric completive self-sorting to give Pd2A2B2 and Pd2A2C2 by variation of the ligand ratio. Cage-to-cage transformations were followed by NMR and MS experiments. Single crystal X-ray structures for three new heteroleptic cages were obtained, impressively highlighting the versatility of ligand A to either form a π-stacked trans-figure-of-eight arrangement in Pd2A2B2 or occupy two cis-edges in Pd2A2C2 or only a single edge in Pd2AB2C. This study paves the way toward the control of heteroleptic cage populations in a systems chemistry context with emerging features such as chemical information processing, adaptive guest selectivity, or stimuli-responsive catalytic action.

Ligand Conformation Controls Assembly of a Helicate/Mesocate, Heteroleptic [Pd2L2L'2] Cages and a Six-Jagged [Pd6L12] Ring.

Molecular building blocks, capable of adopting several strongly deviating conformations, are of particular interest in the development of stimuli-responsive self-assemblies. The pronounced structural flexibility of a short acridone-based bridging ligand, equipped with two monodentate isoquinoline donors, is herein exploited to assemble a surprisingly diverse series of coordination-driven Pd(II) architectures. First, it can form a highly twisted Pd2L4 helicate, transformable into the corresponding mesocate, controlled by temperature, counter anion and choice of solvent. Second, it also allows the formation of heteroleptic cages, either from a mix of ligands with Pd(II) cations or by cage-to-cage transformation from homoleptic assemblies. Here, the acridone-based ligand tolerates counter ligands that carry their donors either in a diverging or converging arrangement, as it can rotate its own coordination sites by 90° and structurally adapt to both situations via shape complementarity. Third, by a near 180° rotation of only one of its arms, the ligand can adopt an S-shape conformation and form an unprecedented C6h-symmetric Pd6L12 saw-toothed six-membered ring.

Non-Templated Assembly of D5h-Symmetric Pd5L10 Rings by Precise Ligand Angle Adjustment.

We report a series of Pd(II)nL2n coordination rings for which nuclearity is controlled by the binding angle of the corresponding bis-monodentate bridging ligands. Judicious choice of the angle within a family of rather rigid ligands allowed for the first-time to synthesize a homoleptic five-membered Pd5L10 ring that does not require any template to form. We demonstrate that control over the ring size is maintained both in the solid-, solution-, and gas-phase. Two X-ray structures of five-membered rings from ligands with ideal angles (yielding a perfect pentagonal ring) vs. suboptimal angles (resulting in a highly distorted structure) illustrate the importance of the correct ligand geometry. A mathematical model for estimating the expected ring size based on the ligand angle was derived and DFT computations show that ring-strain is the major factor determining the assembly outcome.

Shape-Complementary Multicomponent Assembly of Low-Symmetry Co(III)Salphen-Based Coordination Cages.

While metal-mediated self-assembly is a popular technique to construct discrete nanosized objects, highly symmetric structures, built from one type of ligand at a time, are dominating reported systems. The tailored integration of a set of different ligands requires sophisticated approaches to avoid narcissistic separation or formation of statistical mixtures. Here, we demonstrate how the combination of three structure-guiding effects (metal-templated macrocyclization, additional bridging ligands and shape-complementarity) based on Co(III)salphen metal nodes allows for a rational and high-yielding synthesis of structurally complex, lantern-shaped cages with up to four differentiable bridges. Three new heteroleptic coordination cages based on dinuclear Co(III)salphen macrocycles were synthesized in a one-pot reaction approach and fully characterized, including single crystal X-ray analyses. One cage groups two of the same ligands, another two different ligands around a symmetric Co2-bis-salphen ring. In the most complex structure, this ring is unsymmetric, rendering all four connections between the two metal centers distinguishable. While heteroleptic assembly around Pd(II) nodes has been shown to be dynamic, beneficial for cage-to-cage transformations, assembly cascades and adaptive systems, the herein introduced cages based on kinetically more inert Co(III)salphen will be advantageous for applications in enzyme-like catalysis and molecular machinery that require enhanced structural and chemical stability.

Ring-Size Control and Guest-Induced Circularly Polarized Luminescence in Heteroleptic Pd3A3B3 and Pd4A4B4 Assemblies.

Two new structural motifs within the class of heteroleptic PdnAnBn assemblies, namely syn-cis-Pd3A3B3 bowls and bowl- (syn) or saddle- (anti) shaped cis-Pd4A4B4 rings are introduced. All of the ten examples share a common longer fluorenone-based bis-monodentate ligand, equipped with meta-pyridine donor groups. The ring size (3- vs. 4-membered) and conformational preference (bowl vs. saddle) are controlled by the choice of the shorter ligand. These carry para-pyridine donors, different aromatic backbones (benzene, thiophene or selenophene) and either no or small or bulky endohedral substituents, serving to control the nuclearity of the heteroleptic rings through different effects (ligand angle, charge distribution or backbone bulk). Moreover, the luminescence of the fluorenone ligand is conserved in the formed architectures. Emission intensity as well as host-guest properties vary depending on the inward-pointing functions. All Pd3A3B3 assemblies are shown to bind chiral guest BINOL bis-sulfonate which imparts its chirality to the entire host-guest complex. This results in a guest-induced circular dichroism (CD) and circularly polarized luminescence (CPL) with dissymmetry factor glum up to 10-3.

Guest-Induced Reversible Transformation between an Azulene-Based Pd2L4 Lantern-Shaped Cage and a Pd4L8 Tetrahedron.

Azulene, a blue structural isomer of naphthalene, is introduced as the backbone for a new family of Pd(II)-based self-assemblies. Three organic ligands, equipped with varying donor groups, produce three [Pd2L4] cages of different cavity dimensions. Unexpectedly, the addition of organic disulfonate guests to the smallest lantern-shaped cage (featuring pyridine donors) led to a rapid and quantitative transformation to a distorted-tetrahedral [Pd4L8] species. On the contrary, [Pd2L4] cages formed from ligands with isoquinoline donors either just encapsulated the guests or showed no interaction. The tetrahedral species could be fully reverted back to its original [Pd2L4] topology by capturing the guest by another, stronger binding [Pd2L'4] coordination cage, narcissistically self-sorting from the first cage. The azulenes, serving as colored hydrocarbon backbones of minimal atom count, allow one to follow cage assembly and guest-induced transformation by the naked eye. Furthermore, we propose that their peculiar electronic structure influences the system's assembly behavior.

Guest Encapsulation Alters the Thermodynamic Landscape of a Coordination Host.

The architecture of self-assembled host molecules can profoundly affect the properties of the encapsulated guests. For example, a rigid cage with small windows can efficiently protect its contents from the environment; in contrast, tube-shaped, flexible hosts with large openings and an easily accessible cavity are ideally suited for catalysis. Here, we report a "Janus" nature of a Pd6L4 coordination host previously reported to exist exclusively as a tube isomer (T). We show that upon encapsulating various tetrahedrally shaped guests, T can reconfigure into a cage-shaped host (C) in quantitative yield. Extracting the guest affords empty C, which is metastable and spontaneously relaxes to T, and the T⇄C interconversion can be repeated for multiple cycles. Reversible toggling between two vastly different isomers paves the way toward controlling functional properties of coordination hosts "on demand".

Structure and Flexibility of Copper-Modified DNA G-Quadruplexes Investigated by 19 F ENDOR Experiments at 34†GHz.

DNA G-quadruplexes (GQs) are of great interest due to their involvement in crucial biological processes such as telomerase maintenance and gene expression. Furthermore, they are reported as catalytically active DNAzymes and building blocks in bio-nanotechnology. GQs exhibit remarkable structural diversity and conformational heterogeneity, necessitating precise and reliable tools to unravel their structure-function relationships. Here, we present insights into the structure and conformational flexibility of a unimolecular GQ with high spatial resolution via electron-nuclear double resonance (ENDOR) experiments combined with Cu(II) and fluorine labeling. These findings showcase the successful application of the 19 F-ENDOR methodology at 34 GHz, overcoming the limitations posed by the complexity and scarcity of higher-frequency spectrometers. Importantly, our approach retains both sensitivity and orientational resolution. This integrated study not only enhances our understanding of GQs but also expands the methodological toolbox for studying other macromolecules.

Substitution Effects on the Photophysical and Photoredox Properties of Tetraaza[7]helicenes.

A series of substituted derivatives of tetraaza[7]helicenes were synthesized and the influence of the substitution on their photophysical and photoredox-catalytic properties was studied. The combination of their high fluorescence quantum yields of up to 0.65 and their circularly polarized luminescence (CPL) activity results in CPL brightness values (BCPL ) that are among the highest recorded for [7]helicenes so far. A sulfonylation/hetarylation reaction using cyanopyridines as substrates for photoinduced electron transfer (PET) from the excited helicenes was conducted to test for viability in photoredox catalysis. DFT calculations predict the introduction of electron withdrawing substituents to yield more oxidizing catalysts.

Towards Fast Circularly Polarized Luminescence in 2-Coordinate Chiral Mechanochromic Copper(I) Carbene Complexes.

A series of chiral mechanochromic copper(I) cAAC (cAAC=cyclic (alkyl)(amino)carbene) complexes with a variety of amide ligands have been studied with regard to their photophysical and chiroptical properties to elucidate structure-property relationships for the design of efficient triplet exciton emitters exhibiting circularly polarized luminescence. Depending on the environment, which determines the excited state energies, either thermally activated delayed fluorescence (TADF) from 1/3 LLCT states or phosphorescence from 3 LLCT/LC states occurs. However, neither chiral moieties at the carbene nor at the carbazolate ligands provide detectable luminescence dissymmetries glum . An exception is [Cu(phenoxazinyl)(cAAC)], showing orange to deep red TADF with λmax =601-715 nm in solution, powders and in PMMA. In this case, the amide ligand can undergo distortions in the excited state. This design motif leads to the first linear, non-aggregated CPL-active copper(I) complex with glum of -3.4 ⋅ 10-3 combined with a high radiative rate constant of 6.7 ⋅ 105  s-1 .

Engineering Soluble Diketopyrrolopyrrole Chromophore Stacks from a Series of Pd(II)-Based Ravels.

A strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non-statistical metallosupramolecular self-assembly is introduced. For this, the DPP backbone is equipped with nitrogen-based donors that allow for different discrete assemblies to be formed upon the addition of Pd(II), distinguished by the number of π-stacked chromophores. A Pd3 L6 three-ring, a heteroleptic Pd2 L2 L'2 ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self-penetrated motifs (a Pd2 L3 triple and a Pd2 L4 quadruple stack), were obtained and systematically investigated. With increasing counts of stacked chromophores, UV/Vis absorptions red-shift and emission intensities decrease, except for compound Pd2 L2 L'2 , which stands out with an exceptional photoluminescence quantum yield of 51 %. This is extraordinary for open-shell metal containing assemblies and explainable by an intra-assembly FRET process. The modular design and synthesis of soluble multi-chromophore building blocks offers the potential for the preparation of nanodevices and materials with applications in sensing, photo-redox catalysis and optics.

Light-Powered Dissipative Assembly of Diazocine Coordination Cages.

Stimuli-responsive coordination cages allow reversible control over guest binding and release, relevant for adaptive receptors, carriers, catalysts, and complex systems. Light serves as an advantageous stimulus, as it can be applied with precise spatial and temporal resolution without producing chemical waste products. We report the first Pd-mediated coordination cage based on ligands embedding a diazocine photoswitch. While the thermodynamically more stable cis-photoisomer sloppily assembles to a mixture of species with general formula [Pdncis-L2n], the less stable trans-isomer yields a defined [Pd2trans-L4] cage that reversibly converts back to the cis-system by irradiation at 530 nm or thermal relaxation. The [Pdncis-L2n] species do not bind a given guest; however, [Pd2trans-L4] is able to encapsulate a bis-sulfonate as long as it is kept assembled, requiring continuous irradiation at 385 nm. In the absence of UV light, thermal relaxation results in back-switching and guest release. Assembly and properties of the system were characterized by a combination of NMR, ion mobility ESI-MS, single-crystal X-ray diffraction, and UV-vis absorption studies.

Nonaqueous Emulsion Polycondensation Enabled by a Self-Assembled Cage-like Surfactant.

Nonaqueous emulsions are crucial for a range of applications based on water-sensitive systems such as controlled polymerizations requiring anhydrous reaction conditions and the stabilization of readily hydrolyzable reagents or pharmacologically active components. However, defined molecular surfactants to stabilize such nonaqueous emulsions are scarce. We introduce a self-assembled coordination cage, decorated with cholesterol functionalities, to serve as a molecular surfactant for various oil-in-oil emulsions of immiscible organic solvents. While the positively charged cage forms the amphiphile's polar moiety, the non-polar cholesterol appendices can bend in a common direction to stabilize the emulsion. Templated by the droplets, polycondensation reactions were carried out to produce microstructured polyurethane and polyurea materials of different particle sizes and morphologies. Further, the amphiphilic cage can encapsulate a guest molecule and the resulting host-guest assembly was also examined as a surfactant. In addition, the aggregation behavior of the amphiphilic cage in an aqueous medium was examined.

Phosphorescence Induction by Host-Guest Complexation with Cyclodextrins - The Role of Regioisomerism and Affinity.

We present an in-depth investigation of cyclodextrin complexes with guest compounds featuring complexation-induced room temperature phosphorescence (RTP) in aqueous solution. Very interestingly, only the complexed regioisomers bearing lateral substituents on meta-position show RTP, whereas the stronger host-guest systems with para-substituted dyes show no RTP features. The reported systems were investigated regarding their complexation behavior in water using isothermal titration calorimetry and mass spectrometry. In the case of γ-CD very strong 1 : 1 inclusion complexes (Ka up to 5.13×105  M-1 ) were unexpectedly observed. It was found that not only a strong binding to the cyclodextrin cavity is needed to restrict motion, inducing the emission, but also the conformation inside the cavity plays a pivotal role - as supported by an extensive NMR study and MD simulations.

Coordination Cage-Based Emulsifiers: Templated Formation of Metal Oxide Microcapsules Monitored by In Situ LC-TEM.

Metallo-supramolecular self-assembly has yielded a plethora of discrete nanosystems, many of which show competence in capturing guests and catalyzing chemical reactions. However, the potential of low-molecular bottom-up self-assemblies in the development of structured inorganic materials has rarely been methodically explored so far. Herein, we present a new type of metallo-supramolecular surfactant with the ability to stabilize non-aqueous emulsions for a significant period. The molecular design of the surfactant is based on a heteroleptic coordination cage (CGA-3; CGA=Cage-based Gemini Amphiphile), assembled from two pairs of organic building blocks, grouped around two Pd(II) cations. Shape-complementarity between the differently functionalized components generates discrete amphiphiles with a tailor-made polarity profile, able to stabilize non-aqueous emulsions, such as hexadecane-in-DMSO. These emulsions were used as a medium for the synthesis of spherical metal oxide microcapsules (titanium oxide, zirconium oxide, and niobium oxide) from soluble, water-sensitive alkoxide precursors by allowing a controlled dosage of water to the liquid-liquid phase boundary. Synthesized materials were analyzed by a combination of electron microscopic techniques. In situ liquid cell transmission electron microscopy (LC-TEM) was utilized for the first time to visualize the dynamics of the emulsion-templated formation of hollow inorganic titanium oxide and zirconium oxide microspheres.

Guest-Modulated Circularly Polarized Luminescence by Ligand-to-Ligand Chirality Transfer in Heteroleptic PdII Coordination Cages.

Multicomponent metallo-supramolecular assembly allows the rational combination of different building blocks. Discrete multifunctional hosts with an accessible cavity can be prepared in a non-statistical fashion. We employ our shape-complementary assembly (SCA) method to achieve for the first time integrative self-sorting of heteroleptic PdII cages showing guest-tunable circularly polarized luminescence (CPL). An enantiopure helicene-based ligand (M or P configuration) is coupled with a non-chiral emissive fluorenone-based ligand (A or B) to form a series of Pd2 L2 L'2 assemblies. The modular strategy allows to impart the chiral information of the helicenes to the overall supramolecular system, resulting in CPL from the non-chiral component. Guest binding results in a 4-fold increase of CPL intensity. The principle offers potential to generate libraries of multifunctional materials with applications in molecular recognition, enantioselective photo-redox catalysis and information processing.

Steering the Ultrafast Opening and Closure Dynamics of a Photochromic Coordination Cage by Guest Molecules.

Photochemical studies on supramolecular hosts that can encapsulate small guest molecules commonly focus on three aspects: photoswitching the cage to release or trap the guest, the effect of the confining environment on the guest, and light-induced exciton or charge transfer within the cage structure. Here, we exploit ultrafast spectroscopy to address how the guest alters the photoswitching characteristics of the cage. For this, the impacts of three disparate guest compounds on ring-opening or ring-closure of a dithienylethene (DTE) ligand in a photoswitchable DTE-based coordination cage are juxtaposed. The guest modulates both outcome and timescale of the cage's photodynamics, by an interplay of structural strain, heavy-atom effect, and enhancement of charge-transfer processes exercised by the guest on the photo-excited cage. The approach might prove beneficial for attuning the applicability of photoswitchable nanocontainers and desired guest compounds.

LiBF4 -Induced Rearrangement and Desymmetrization of a Palladium-Ligand Assembly.

Thirteen palladium-ligand assemblies with different structures and topologies were investigated for the ability to bind lithium ions. In one case, the addition of LiBF4 resulted in a profound structural rearrangement, converting a dincluclear [Pd2 L4 ]4+ complex into a low-symmetry [Pd4 L8 ]8+ assembly with two binding pockets for solvated LiBF4 ion pairs. The rearrangement could only be induced by Li+ , indicating highly specific host-guest interactions. A structural analysis of the [Pd4 L8 ]8+ receptor revealed a compact structure with multiple intramolecular interactions, reminiscent of what is seen for natural and synthetic foldamers.

Endohedrally Functionalized Heteroleptic Coordination Cages for Phosphate Ester Binding.

Metallosupramolecular hosts of nanoscopic dimensions, which are able to serve as selective receptors and catalysts, are usually composed of only one type of organic ligand, restricting diversity in terms of cavity shape and functional group decoration. We report a series of heteroleptic [Pd2 A2 B2 ] coordination cages that self-assemble from a library of shape complementary bis-monodentate ligands in a non-statistical fashion. Ligands A feature an inward pointing NH function, able to engage in hydrogen bonding and amenable to being functionalized with amide and alkyl substituents. Ligands B comprise tricyclic aromatic backbones of different shape and electronic situation. The obtained heteroleptic coordination cages were investigated for their ability to bind phosphate diesters as guests. All-atom molecular dynamics (MD) simulations in explicit solvent were conducted to understand the mechanistic relationships behind the experimentally determined guest affinities.

Integrative Assembly of Heteroleptic Tetrahedra Controlled by Backbone Steric Bulk.

A bent fluorenone-based dipyridyl ligand LA reacts with PdII cations to a solvent-dependent dynamic library of [PdnL2n] assemblies, constituted by a [Pd3LA6] ring and a [Pd4LA8] tetrahedron as major components, and a [Pd6LA12] octahedron as minor component. Introduction of backbone steric hindrance in ligand LB allows exclusive formation of the [Pd6LB12] octahedron. Combining equimolar amounts of both ligands results in integrative self-sorting to give an unprecedented [Pd4LA4LB4] heteroleptic tetrahedron. Key to the non-statistical assembly outcome is exploiting the structural peculiarity of the [Pd4L8] tetrahedral topology, where the four lean ligands occupy two doubly bridged edges and the bulky ligands span the four remaining, singly bridged edges. Hence, the system finds a compromise between the entropic drive to form an assembly smaller than the octahedron and the enthalpic prohibition of pairing two bulky ligands on the same edge of the triangular ring. The emission of luminescent LA is maintained in both homoleptic [Pd3LA6] and heteroleptic [Pd4LA4LB4].