Molecular Triangles Research Articles

Leveraging Halogen Interactions for a Supramolecular Nanotube.

We demonstrate the formation of supramolecular nanotubes from molecular triangles in a single crystal by balancing the hydrogen bonds and halogen interactions between individual macrocycles. Thereby, we template the supramolecular nanotube growth by intermolecular interactions encoded directly in the macrocycles instead of those provided by the crystallization solvent. Ultimately, we show that replacing bromines for iodines in the macrocycle is necessary to achieve this supramolecular organization by enhancing the strength of the halogen interactions and concomitant reduction of the detrimental hydrogen bonds. We investigated the nature and the interplay of the individual intermolecular interactions by analysis of the experimental single crystal data and quantum chemical calculations. This work enriches the available toolbox of supramolecular interactions and will aid and abet the development of rationally-designed materials with a long-range 1D tubular organization.

Matrix effects on the magnetic properties of a molecular spin triangle embedded in a polymeric film.

Molecular triangles with competing Heisenberg interactions and significant Dzyaloshinskii-Moriya interactions (DMI) exhibit high environmental sensitivity, making them potential candidates for active elements for quantum sensing. Additionally, these triangles exhibit magnetoelectric coupling, allowing their properties to be controlled using electric fields. However, the manipulation and deposition of such complexes pose significant challenges. This work explores a solution by embedding iron-based molecular triangles in a polymer matrix, a strategy that offers various deposition methods. We investigate how the host matrix alters the magnetic properties of the molecular triangle, with specific focus on the magnetic anisotropy, aiming to advance its practical applications as quantum sensors.

Search for Toroidal Ground State and Magnetoelectric Effects in Molecular Spin Triangles with Antiferromagnetic Exchange

Using first-principles methods and spin models, we investigate the magnetic properties of transition-metal trimers Cr3 and Cu3. We calculate exchange coupling constants and zero-field splitting parameters using density functional theory and, with these parameters, determine the ground spin state as well as thermodynamic properties via spin models. Results for Cr3 indicate uniaxial magnetic anisotropy with a magnetic easy axis aligned along the 3-fold rotational symmetry axis and a mostly isotropic exchange interaction. The Cu3 molecule lacks rotational symmetry and our results show strong antisymmetric interactions for three distinct exchange couplings within the molecule. We are able to reproduce experimental findings on magnetic susceptibility and magnetization of Cr3 with the first-principles spin-Hamiltonian parameters. Our results show no presence of a toroidal ordering of spins for Cr3 and a finite toroidal moment for Cu3 in the ground state. We apply an external electric field up to 0.08 V/Å to each system to reveal the field dependence of exchange coupling as magnetoelectric effects. Finally, we scan the parameter space of a spin Hamiltonian to gain insights into which parameters would lead to a sizable toroidal moment in such systems.

Solvent and Counteranion Assisted Dynamic Self-Assembly of Molecular Triangles and Tetrahedral Cages.

Self-assembly of naked PdII ions separately with newly designed bis(3-pyridyl)benzothiadiazole (L1) and bis(3-pyridyl)thiazolo[5,4-d]thiazole (L2) donors separately, under varying experimental conditions, yielded Pd4L8 (L= L1 or L2) tetrahedral cages and their homologous Pd3L6 (L= L1 or L2) double-walled triangular macrocycles. The resulting assemblies exhibited solvent, temperature, and counteranion induced dynamic equilibrium. Treatment of L1 with Pd(BF4)2 in acetonitrile (ACN) resulted in selective formation of a tetrahedral cage [Pd4(L1)8](BF4)8 (1a), which is in dynamic equilibrium with its homologue triangle [Pd3(L1)6](BF4)6 (2a) in dimethyl sulfoxide (DMSO). On the other hand, similar self-assembly using L2 instead of L1 yielded an equilibrium mixture of tetrahedral cage [Pd4(L2)8](BF4)8 (3a) and triangle [Pd3(L2)6](BF4)6 (4a) forms in both ACN and DMSO. The assembles were characterized by multinuclear NMR and ESI-MS while the structure of the tetrahedral cage (1a) was determined by single crystal X-ray diffraction. Existence of a dynamic equilibrium between the assemblies in solution has been investigated via variable temperature 1H NMR. The equilibrium constant K = ([Pd4L8]3/[Pd3L6]4) was calculated at each experimental temperature and fitted with the Van't Hoff equation to determine the standard enthalpy (ΔH°) and entropy (ΔS°) associated with the interconversion of the double-walled triangle to tetrahedral cage. The thermodynamic feasibility of structural interconversion was analyzed from the change in ΔG°, which suggests favorable conversion of Pd3L6 triangle to Pd4L8 cage at elevated temperature for L1 in DMSO and L2 in ACN. Interestingly, similar self-assembly reactions of L1 and L2 with Pd(NO3)2 instead of Pd(BF4)2 resulted in selective formation of a tetrahedral cage [Pd4(L1)8](NO3)8 (1b) and double-walled triangle [Pd3(L2)6](NO3)6 (4b), respectively.

Molecular Triangles: A New Class of Macrocycles

ConspectusMacrocycles have had a profound influence on the establishment of supramolecular chemistry because of their abundant molecular recognition and self-assembly characteristics. The design of new macrocyclic receptors that can be tailored by synthesis to display new and exotic properties is an important research objective for chemists and materials scientists. Rigid macrocycles with π-conjugated aromatic units, in contrast with flexible ones, tend to possess large interior and exterior π-surfaces in addition to persistent shapes. These features not only endow these macrocycles with a wide range of host-guest properties but also render them ideal building blocks for constructing a diverse variety of supramolecular architectures. The incorporation of π-conjugated units into macrocycles also imbues them with a wealth of optical, electronic, and magnetic properties, resulting in their broad application in materials science and molecular nanotechnology.Recently, we have designed and synthesized a new class of macrocycles, namely, molecular triangles, which have rigid structures with triangular geometries. They consist of three chiral trans-1,2-cyclohexano apexes and three aromatic tetracarboxylic diimide linkers, such as pyromellitic diimide, naphthalene diimide, and perylene diimide. Benefiting from the availability of facile synthetic protocols, the geometries and properties of these rigid molecular triangles can be altered at will. By combining these tetracarboxylic diimide linkers, we have been able to synthesize both molecular equilateral and isosceles triangles. During the past few years, we have conducted research in a systematic manner on the structural features and self-assembly characteristics of these molecular triangles. The following points are worthy of note regarding these molecular triangles: (i) They possess shape-persistent inner cavities of a highly electron-deficient nature. These features endow them with the ability to complex with anions and electron-rich molecules, forming supramolecular nanotubes and two-dimensional tilings. (ii) Those with intrinsic chirality are able to self-assemble into solid-state nonhelical or single-handed helical superstructures, inducing selective chirality transfer from the macrocycles to their crystalline supramolecular assemblies. (iii) The triangular arrangement of aromatic tetracarboxylic diimide linkers contributes to through-space electron delocalization encompassing the entire macrocycle, conferring exotic electronic and spin properties. To date, the family of molecular triangles has exhibited a range of physicochemical properties, such as anion recognition, chiral assembly, supramolecular gelation, energy storage, solid-state luminescence, and nonlinear optical response.In this Account, we summarize our recent progress in research into these molecular triangles. We present an overview of their design and synthesis, as well as a general summary of their structural features. Thereafter, we discuss state-of-the-art developments in relation to their molecular recognition properties and their assembly characteristics. In addition, we highlight the potential applications of these molecular triangles and their complexes with a range of solvents and electron-rich molecules. Finally, we speculate on further structural modifications and application-oriented explorations based on this class of molecular triangles.

What is the driving force behind molecular triangles and their guests? A quantum chemical perspective about host-guest interactions.

The physical nature of host-guest (HG) interactions occurring between molecular triangles and linear anions was explored using density functional theory (DFT) calculations combined with energy decomposition analyses (EDA), nuclear independent chemical shift (NICS), and non-covalent interaction index (NCI). We demonstrate that: (i) in addition to the host being significantly rigid, the strain energies are not negligible, especially for host 2; (ii) halogen anions interact mainly by electrostatic forces (ΔEelst > ΔE > ΔEdisp), meanwhile; (iii) trihalogen anions interact mostly by dispersion forces (ΔEdisp > ΔEelst≈ΔE). The NICS and NCI calculations corroborate the idea that HG interactions are considerably mediated through dispersion terms, and also indicate an antiaromatic character inside the host walls.

Self‐Assembly Reactions To Form Multinuclear Zirconium(III) and Titanium(III) Complexes with Imidazole Derivatives as Bridging Ligands

Self‐assembly reactions with low valent early transition metals, leading to neutral multinuclear complexes are rare. Mostly late transition metals like Pt, Pd or Ru together with N‐heterocycles or O‐donor‐based ligands are used to form supramolecular coordination complexes. This paper reports on self‐assembly reactions of low valent titanocene and zirconocene units and five‐membered N‐heterocycles as bridging ligands. These reactions lead to novel molecular triangles and rectangles with the metal centers marking the vertices. Five different imidazole derivatives and four different metallocene precursors were used. For the first time, molecular triangles and architectures with zirconocene as vertex units through self‐sorting effects are reported. Less sterically demanding substituents lead to the formation of molecular rectangles, whereas more sterically demanding substituents, e.g. Cp*‐ligands on the metal centers or phenyl groups on the bridging ligands lead to the formation of molecular triangles. The synthesis and properties of these air and moisture sensitive compounds are shown and discussed, and their molecular structures and geometries in the solid state were determined by single‐crystal X‐ray diffraction.

Lanthanide Triangles Supported by Radical Bridging Ligands.

The first examples of metallacycles containing rare earth ions bridged by radicals are reported. The molecular triangles [Ln3(hfac)6(bptz•-)3] (Ln = DyIII, YIII; hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) consist of lanthanide ions bridged by bptz radical anion (bptz•-) ligands. Magnetic susceptibility measurements and CASSCF calculations performed on [Dy3(hfac)6(bptz•-)3] reveal the presence of antiferromagnetic coupling between the DyIII centers and the bptz•- ligands, with J = -6.62 cm-1.

Charge Effect on the Formation of Polyoxometalate-Based Supramolecular Polygons Driven by Metal Coordination

The metal-driven self-assembly of a Keggin-based hybrid bearing two remote pyridine units was investigated. The resulting supramolecular species were identified by combination of 2D diffusion NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS) as a mixture of molecular triangles and squares. This behavior is different from that of the structural analogue Dawson-based hybrid displaying a higher charge, which only led to the formation of molecular triangles. This study highlights the decisive effect of the charge of the POMs in their self-assembly processes that disfavors the formation of large assemblies. An isothermal titration calorimetry (ITC) experiment confirmed the stronger binding in the case of the Keggin hybrids. A correlation between the diffusion coefficient D and the molecular mass M of the POM-based building block and its coordination oligomers was also observed. We show that the diffusion coefficient of these compounds is mainly determined by their occupied volume rather than by their shape.

Versatility of Two Diimidazole Building Blocks in Coordination-Driven Self-Assembly.

A series of discrete molecular architectures was synthesized via self-assembly of two "linear" diimidazole donors [L1 = 1,4-di(1H-imidazol-1-yl)benzene and L2 = 1,1'-(2,5-dimethyl-1,4-phenylene)bis(1H-imidazole)] independently with cis-[(tmeda)Pd(NO3)2] [tmeda = N,N,N',N'-tetramethylethane-1,2-diamine], cis-[(tmeda)Pt(NO3)2], a diplatinum(II) acceptor (bisPt), and Pd(NO3)2. The donors L1 and L2 are isostructural with four hydrogens in the benzene ring of L1, whereas in L2 two of such hydrogens are substituted by methyl groups. The assemblies were characterized by NMR spectroscopy and electrospray ionization mass spectrometry analyses along with single-crystal structure determination of three of them. While the self-assembly of L1 with cis-[(tmeda)Pd(NO3)2] solely formed a [3 + 3] self-assembled molecular triangle (1), L2 with the same acceptor predominantly resulted in the formation of a [4 + 4] molecular square (3). Such a dramatic change in the final outcome in the coordination-driven self-assembly by simple alkyl substitution of isostructural donors is remarkable. Interestingly, self-assembly of L1 and L2 with analogous Pt(II) acceptor cis-[(tmeda)Pt(NO3)2] yielded mixtures of [3 + 3] triangle and [4 + 4] square, where the molecular triangles (4 and 6) were the predominant products in both the cases. The same donors in combination with a 0° acceptor bisPt independently formed the expected [2 + 2] metallo-macrocycles (8 and 9). Surprisingly, the macrocycle (9) involving L2 is found to exist in more than one conformation at room temperature. Moreover, the diimidazole donors formed unprecedented Pd6L12 molecular spheres (10 and 11) when they were separately treated with Pd(NO3)2. The imidazole moieties in the ligands are found to appear in versatile orientations in the synthesized molecules due to their rotational flexibility to produce required bite angles for the particular architecture.

In situ generated polysiloxanes stabilizing μ3-oxo bridged Sb3 triangles.

The reaction of RSbO3H2 with t-butylsilanetriol has led to the isolation of organoantimony(v) based molecular triangles stabilized by siloxane frameworks. Depending on the reaction conditions employed or the substituents present on the antimony atom, either a combination of a disiloxane and a tetrasiloxane framework or a trisiloxane framework was generated in situ leading to the stabilization of the Sb3 triangle.

Reversible Mechanical Interlocking of D-Shaped Molecular Karabiners bearing Coordination-Bond Loaded Gates: Route to Self-Assembled [2]Catenanes.

Complexation of 1,4-phenylenebis(methylene) diisonicotinate, L1, with cis-protected Pd(II) components, [Pd(L')(NO3 )2 ], in an equimolar ratio yielded binuclear complexes, 1 a-d of [Pd2 (L')2 (L1)2 ](NO3 )4 formulation where L' stands for ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), and phenanthroline (phen). The combination of 4,4'-bipyridine, L2, with the cis-protected Pd(II) units is known to yield molecular squares, 2 a-d. However, 2 b-d coexist with the corresponding molecular triangles, 3 b-d. Combination of an equivalent each of the ligands L1 and L2 with two equivalents of cis-protected Pd(II) components in DMSO resulted in the D-shaped heteroligated complexes [Pd2 (L')2 (L1)(L2)](NO3 )4 , 4 a-d. Two units of the D-shaped complexes interlock, in a concentration dependent fashion, to form the corresponding [2]catenanes [Pd2 (L')2 (L1)(L2)]2 (NO3 )8 , 5 a-d under aqueous conditions. Crystal structures of the macrocycle [Pd2 (tmeda)2 (L1)(L2)](PF6 )4 , 4 b'', and the catenane [Pd2 (bpy)2 (L1)(L2)]2 (NO3 )8 , 5 c, provide unequivocal support for the proposed molecular architectures.

Role of peripheral phenanthroline groups in the self-assembly of self-assembled molecular triangles

Self-assembled molecular triangles [Pd3(phen)3(imidazolate)3](NO3)3, 1a and [Pd3(phen)3 (imidazolate)3](PF6)3, 1b are prepared by the combination of imidazole with Pd(phen)(NO3)2 and Pd(phen) (PF6)2, respectively. Imidazole was deprotonated during the complexation reactions and the imidazolate so formed acted as a bis-monodentate bridging ligand to form the bowl-shaped trinuclear architectures of 1a/b. Relative orientation of the imidazolate moieties can be best described as syn,anti,antias observed in the crystal structure of 1b. However, in solution state, slow conformational changes are assumed on the basis of 1HNMR spectral data. The molecular triangles are crafted with three peripheral phen units capable of π−π stacking interactions. Well-fashioned intermolecular π−π interactions are observed in the solid-state, wherein further self-assembly of already self-assembled triangle is observed. Self-assembly of the self-assembled molecular triangle [Pd3(phen)3(imidazolate)3](PF6)3 is observed in the solid-state where the triangular panels are packed by utilizing intermolecular π−π interactions in a chain like fashion.

One-pot synthesis and AFM imaging of a triangular aramide macrocycle.

Macrocyclizations in exceptionally good yields were observed during the self-condensation of N-benzylated phenyl p-aminobenzoates in the presence of LiHMDS to yield three-membered cyclic aramides that adopt a triangular shape. An ortho-alkyloxy side chain on the N-benzyl protecting group is necessary for the macrocyclization to occur. Linear polymers are formed exclusively in the absence of this Li-chelating group. A model that explains the lack of formation of other cyclic congeners and the demand for an N-(o-alkoxybenzyl) protecting group is provided on the basis of DFT calculations. High-resolution AFM imaging of the prepared molecular triangles on a calcite(10.4) surface shows individual molecules arranged in groups of four due to strong surface templating effects and hydrogen bonding between the molecular triangles.

Self-assembly of self-assembled molecular triangles

A rare variety of self-assembled molecular triangle [Pd3(bpy)3(imidazolate)3](NO3)3, 1 is prepared by the combination of Pd(bpy)(NO3)2 with imidazole, at 1:1 ratio, in acetonitrile-water. Deprotonation of imidazole happened during the course of the complexation reaction where upon the metallomacrocycle is formed. The bowl-shaped trinuclear architecture of 1 is crafted with three peripheral bpy units capable of π−π stacking interactions. While the solution state structure of 1can be best described as a trinuclear complex, in the solid-state well-fashioned intermolecular π−π and CH- π interactions are observed. Thus, in the solid-state further self-assembly of already self-assembled molecular triangle is witnessed. The triangular panels are arranged in a linear manner utilizing intermolecular π−π interactions where upon two out of three bpy units of each molecule participated in the chain formation.

Self-Assembled Squares and Triangles by Simultaneous Hydrogen Bonding and Metal Coordination

Through the combination of hydrogen bonding and metal-templated self-assembly, molecular squares and molecular triangles are observed in chloroform solution upon the complexation of hydrogen-bonded dimers of para-pyridyl-substituted 2-ureido-4-[1H]-pyrimidinone (UPy) and an appropriate cis-substituted palladium complex. Molecular modeling studies and NMR analysis confirmed the presence of two distinct structures in solution: the tubular structure of the molecular square and propeller-bowl structure of the molecular triangle.

Dondorff Rings: Synthesis, Isolation, and Properties of 60°‐Directed Bisterpyridine‐Based Folded Tetramers

Square feat: The synthesis, isolation, and characterization of five novel bisterpyridine-based metallomacrocycles, possessing a folded tetrameric configuration is reported (see figure). The initial dimeric building block with the stable linear {tpy-Ru(II)-tpy} connectivity circumvents the formation of the thermodynamically favored molecular triangles.

Effect of ligand flexibility on coordination-driven self-assembly of Pt(II) metallacycles

The effect of ligand flexibility on the self-assembly of Pt(II) metallacycles was investigated. Three diazopyridyl ligands with different flexibilities were used to synthesize three nanoscale supramolecular complexes via Pt(II) mediated self-assembly. With comparatively less flexible ligands, 4,4′azobispyridine (2) and pyridine-4-carbaldehyde azine (3), formation of [3+3] molecular triangles was observed; in contrast, the most flexible of the three ligands, pyridine-3-carbaldehyde azine (4), yielded the [2+2] molecular rhomboid. All three complexes were characterized by multinuclear NMR (1H and 31P) and HR-ESI-MS, and the structure of complex 7 was further established by X-ray crystallography. These studies clearly showed that increased ligand flexibility entropically favors the formation of smaller metallacycles as the ligand can reduce angular strain through bending or conformational change.

Molecular Triangles: Synthesis, Self-Assembly, and Blue Emission of Cyclo-7,10-tris-triphenylenyl Macrocycles

A set of cyclo-7,10-tris-triphenylenyl macrocycles have been prepared by a Yamamoto cyclotrimerization protocol. In these novel macrocycles, three triphenylene units are covalently linked to each other, resulting in the formation of triangular-shaped molecules. The fully planar derivative revealed pronounced self-assembly behavior. NMR spectroscopy was used to determine the association constant in solution. 2D wide-angle X-ray scattering was applied to the study of the liquid crystallinity of this new discotic mesogen in the bulk state. Furthermore, nonplanar, laterally substituted derivatives were successfully tested as blue emitters in organic light-emitting diodes owing to their unique optoelectronic properties and their high stability. In this case, substitution with sterically demanding phenyl groups was efficiently used to suppress intermolecular packing, thus preventing undesired quenching effects.

Mixed-Valency and Metal-Metal Coupling in Polynuclear Metal Complexes: Recent Progress and Prospects

Recent progress in the redox chemistry of multimetallic transition-metal complexes and clusters is reviewed. Special attention is paid to high-nuclearity complexes wherein redox-active sites (e.g., ferrocenyl pendants or Ru centers) are assembled in a close proximity with a well-defined geometry via the covalent or coordination bonds. A special emphasis is placed on literature survey for paddlewheel diruthenium(II,III) complexes coordinated by axial or equatorial ferrocenyl ligands, polyferrocenyl compounds in the form of wire, star, and ring, ferrocenyl-based dendrimers, and ligand-mediated molecular triangles and squares. Finally, future prospects of these mixed-valent systems are briefly discussed.