3D Supramolecular Assembly Research Articles

Cu(II)-Na(I) heterometallic coordination compounds as photocatalyst for degradation of methylene blue

Two new Cu(II)/Na(I) coordination polymers, namely, {[(Cu(L1)Na)2(ox)(ClO4)2]∙dmf}n (1) and {[(Cu(L2)Na)2(nph)]∙H2O}n (2) were synthesized by using the Schiff base N-(2-hydroxyethoxy)ethyl-iminomethyl-phenol (H2L1) with oxalate (ox) and (3-methoxy-2-hydroxybenzylidene)propanoic acid (H2L2) with naphthalene-2,6-dicarboxylate anions (nph), respectively. Both the complexes were characterized using elemental analysis, FT-IR, UV–vis spectroscopic analyses. The solid state structures of complexes 1–2 were determined using single crystal X-ray crystallography that revealed for 1 the presence of dinuclear copper(II) species, [(L1)Cu(ox)Cu(L1)], while 2 consists of stair-like 1D -[CuL2]2-(nph)]n- polymers. Both these fragments are further connected by Na(I) cations to form 2D supramolecular assemblies. In both the compounds the copper and sodium atoms exhibit a square pyramidal and a distorted octahedral coordination geometry, respectively. The catalytic activity of complexes 1–2 for the degradation of methylene blue (MB) was investigated under UV irradiation and in the presence of very small amount of H2O2. Both the compounds were found to be photo-catalytically active, and the mechanism of photocatalysis has been discussed in detail.

Fabrication of a halopyridine appended Co(II) based 1D coordination polymer for efficient charge transportation

A new halopyridine appended Co(II) based coordination polymer (CP), [Co(3-clpy)2(fum)2(H2O)2]n (1) {3-clpy = 3-Chloropyridine and H2fum = fumaric acid} has been synthesized and characterized by elemental analysis and single crystal X-ray diffraction (SCXRD) technique. Compound 1 crystallizes in monoclinic space group P21/c. Herein, the ditopic linker H2fum acts as bridging ligand in the formation of a one dimensional (1D) CP. The 1D chains are interconnected via hydrogen bonding interactions leading to 2D sheet. The 3-clpy ligands of one chain facilitate π⋯π stacking interactions with adjacent chain leading to 3D supramolecular assembly which generally promotes better charge transport in the material. Hirshfeld surface analysis has also been performed to check the non covalent interactions in the crystal packing. Interestingly, the compound 1 shows electrical conductivity and reveals Schottky barrier diode behavior.

Two polyoxometalate-based hybrids constructed from trinuclear lanthanoid clusters with single‐molecule magnet behavior

In this paper we report the successful hydrothermal synthesis of the two inorganic–organic hybrid assemblies H0.87{Na(H2O)3[Dy(PDA)(H2O)2]3(BW12O40)0.87(SiW12O40)0.13}•11H2O (1) and H0.87{Na(H2O)3[Ho(PDA)(H2O)2]3 (BW12O40) 0.87(SiW12O40)0.13}•10H2O (2) (H2PDA = 1,10-phenanthroline-2,9-dicarboxylic acid). Both hybrids have been characterized using elemental analyses, Fourier transform infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Structural characterizations by single-crystal X-ray diffraction reveals that these hybrids are isostructural including [BW12O40]5- Keggin-type polyoxometalates (actually containing 87% B and 13% Si based on refinement of the crystal structures) connected by three lanthanoids to yield discrete trinuclear lanthanoid clusters. These discrete molecules are further packed into 3D supramolecular assemblies by means of hydrogen-bonding and anion–π interactions. 1 and 2 are two examples of a relatively small number of inorganic–organic hybrid POMs containing the PDA ligand based on a CSD search (CSD version 5.40 updated to November 2018). The temperature dependences of χmT for 1 and 2 are considered. Magnetic studies reveal that 1 exhibits typical single‐molecule magnet (SMM) behavior.

Cu(II) coordination polymer bearing diazenyl-benzoic ligand: Synthesis, physico-chemical and XRD/HSA-interactions

New binuclear copper(II) complex [Cu2L2] zig-zag coordination polymer (CCP) have been synthesized via one-pot copper(II) acetate/(E)-2-((2-hydroxynaphthalen-1-yl)diazenyl)benzoic dye through an in situ aqua doubly deprotonated ligand substitution reaction. The coordination polymer complex was characterized by spectroscopic and CHN-elemental analysis. The crystal structure has been specified by the XRD-method exhibiting that the Cu(II) center geometry is with five-coordinated distorted tetragonal pyramidal. The desired CCP structure chains are connected into a 2D-Supramolecular assembly via one C-H…O H-bond and enhanced by a π–π stacking interactions. These interconnections strengthened the lattice of CCP that originated the formation of super thermal CCP complexes. The fundamental vibrational wavenumbers and electron transfer in the free ligand are combined with the complex before and after coordination to demonstrate the spectral behavior of L−2 in the desired zig-zag CCP. The 2D-fingerprint (2D-FP) and Hirshfeld surface analysis (HSA) computations were served to prove the 2D-network packed crystal lattice interactions.

Ultrathin Two Dimensional (2D) Supramolecular Assembly and Anisotropic Conductivity of an Amphiphilic Naphthalene-Diimide.

Two-dimensional (2D)-supramolecular assemblies of π-conjugated chromophores are relatively less common compared to a large number of recent examples on their low dimensional (0D or 1D) assemblies or 3D architectures. This article reports a rational design for the 2D supramolecular assembly of an amphiphilic core-substituted naphthalene-diimide derivative (cNDI-1). The building block contains a naphthalene-diimide (NDI) chromophore, symmetrically substituted with two dodecyl chains from the aromatic core while the imide positions are functionalized with two hydrophilic wedges containing oligo-oxyethylene chains. In water, it exhibits entropically favorable self-assembly with a critical aggregation concentration of 1.5 × 10-5 M and a lower critical solution temperature of 55 °C. The UV/vis absorption spectrum in water shows bathochromically shifted absorption bands compared to that of the monomeric dye in THF, indicating offset π-stacking among the NDI chromophores. C-H symmetric and asymmetric stretching frequencies in the FT-IR spectrum support the presence of organized hydrocarbon chains in trans conformation in the self-assembled state, similar to that in the crystalline n-alkanes, which is further supported by studying the general polarization (GP) values of a noncovalently entrapped Laurdan dye. The atomic force microscopy (AFM) image shows the formation of ultrathin (height < 2.0 nm) ribbons for the spontaneously assembled sample which eventually produces a large-area 2D nanosheet by the lateral organization. The powder X-ray diffraction pattern of the drop-casted film, prepared from the preformed aggregates, reveals sharp peaks that indicate a crystalline lamellar packing along the direction of the 2D growth. Differential scanning calorimetry trace shows the melting of the crystalline alkyl chain domain at T > 75 °C, which destroys the 2D assembly. Local-scale photoconductivity of the ordered 2D assembly, studied by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) technique, reveals an anisotropic conductivity with ∼3 times larger conductivity along the parallel direction compared to that along the perpendicular one.

Anisotropic hygro-expansion in hydrogel fibers owing to uniting 3D electrowriting and supramolecular polymer assembly

Melt electrowriting (MEW) is mostly applied to print complex three-dimensional (3D) structures using traditional, relatively hydrophobic polymers, such as polycaprolactone. Here, we 3D printed a supramolecular hydrophilic polymer into a solid micrometer-sized fiber structure, solely held together via non-covalent interactions. Interestingly, the solid fibers showed anisotropic swelling in a humid environment as demonstrated by the longitudinal and transverse surface strain determined using a novel global digital height correlation algorithm. This anisotropy in swelling is proposed to originate from a shear-induced orientation of crystals packed into lamellae as shown with small-angle x-ray scattering measurements. The MEW fibers were dried after swelling to study structural differences. Remarkably, no differences in nano-structural conformation in the micrometer-sized fibers was observed after swelling and subsequent drying. In conclusion, a free-standing supramolecular polymer-based hydrogel scaffold, displaying anisotropic hygro-expansion, is shown to be produced using MEW. This unique combination of 3D printing, via a top-down approach, and supramolecular polymer chemistry, via a bottom-up approach, provides new ways to introduce anisotropy and hierarchy in aqueous supramolecular systems. This will open the door towards even more complex hierarchical structures with unprecedented properties.

Isonicotinamide-Based Compounds: From Cocrystal to Polymer.

The reaction between [Cu(μ-OAc)(μ-Pip)(MeOH)]2 (1) (OAc = acetate; Pip = 1,3-benzodioxole-5-carboxylate) and isonicotinamide (Isn) in MeOH as solvent yielded two mixture pairs of three compounds: {(HPip)2(Isn) (2), [Cu(Pip)2(Isn)2] (3)} and {(3), {[Cu3(Pip)2(OAc)2(μ-Isn)2(Isn)2(μ-OCH3)2(MeOH)2]·2MeOH}n (4)}. Modifying the reaction conditions (t, T, molar ratio), 2 and 3 have been successfully isolated, whereas 3 and 4 had to be mechanically separated. The recrystallization of 3 in pentanol yielded single crystals of compound [Cu(Pip)2(Isn)2]·C5H11OH (3a). The X-ray crystal structure of 2, 3a, and 4 has been elucidated showing a cocrystal, a monomer, and an unusual coordination polymer, respectively. The Pip ligand exhibited a chelate (3a) or a monodentate (4) coordination mode, but the Isonicotinamide (Isn) ligand is the one that promoted the arrangement of different structures and also mainly directs the formation of the 2D and 3D supramolecular assemblies. All the structures have been analyzed by Hirshfeld surface. In addition, the energy frameworks and lattice energy values of 2 and 3a have been calculated.

A combined experimental and computational study of a supramolecular assembly based on cationic zinc(II)-ethanesulfonate

Abstract Studies based on the role of non-covalent interactions in physical, chemical, and biological phenomena in supramolecular assemblies have gained considerable interest. Herein, we report a supramolecular assembly, [Zn(phen)2(H2O)2](EtSO3)2·2H2O (1) afforded by the reaction of a preformed zincate salt, [Et4N]2[Zn(OSO2Et)4] and 1,10-phenanthroline (phen). Compound 1 has been characterized by FTIR, 1H/13C NMR, elemental analysis, and single-crystal X-ray crystallography. Crystal structure of 1 reveals two different stacking modes (π … π) between the aromatic rings of phen ligands of dicationic moieties, [Zn(phen)2(H2O)2]2+ leading to the formation of one-dimensional (1D) supramolecular motifs. Furthermore, the ability of the ethanesulfonate group to act as prolific H-bond acceptor (O–H⋯O/C–H⋯O type hydrogen bonds) between the water dimer/tetramer, and aromatic phen rings perpetuates 1D cationic units into a 3D supramolecular motif. Density functional theory (DFT) calculations were carried out to understand the relative importance of such interactions by evaluating their individual bonding energies. Additionally, the 3D Hirshfeld surfaces analysis and 2D fingerplots suggested that the assembly is dominated by H⋯H and O⋯H supramolecular contacts. Remarkably, the interplay of secondary interactions between cationic moieties, weakly-coordinating ethanesulfonate anions, and water dimer/tetramers forming a 3D supramolecular assembly has not been reported in the literature earlier.

Synthesis, Structural Characterization and Ligand-Enhanced Photo-Induced Color-Changing Behavior of Two Hydrogen-Bonded Ho(III)-Squarate Supramolecular Compounds.

Two coordination polymers (CPs) with chemical formulas, [Ho2(C4O4)2(C2O4)(H2O)8]·4H2O (1) and [Ho(C4O4)1.5(H2O)3] (2), (C4O42− = dianion of squaric acid, C2O42− = oxalate), have been synthesized and their structures were determined by single-crystal X-ray diffractometer (XRD). In compound 1, the coordination environment of Ho(III) ion is eight-coordinate bonded to eight oxygen atoms from two squarate, one oxalate ligands and four water molecules. The squarates and oxalates both act as bridging ligands with μ1,2-bis-monodentate and bis-chelating coordination modes, respectively, connecting the Ho(III) ions to form a one-dimensional (1D) ladder-like framework. Adjacent ladders are interlinked via O–H⋅⋅⋅O hydrogen bonding interaction to form a hydrogen-bonded two-dimensional (2D) layered framework and then arranged orderly in an AAA manner to construct its three-dimensional (3D) supramolecular architecture. In compound 2, the coordination geometry of Ho(III) is square-antiprismatic eight coordinate bonded to eight oxygen atoms from five squarate ligands and three water molecules. The squarates act as bridging ligands with two coordination modes, μ1,2,3-trismonodentate and μ1,2-bis-monodentate, connecting the Ho(III) ions to form a 2D bi-layered framework. Adjacent 2D frameworks are then parallel stacked in an AAA manner to construct its 3D supramolecular architecture. Hydrogen bonding interactions between the squarate ligands and coordinated water molecules in 1 and 2 both play important roles on the construction of their 3D supramolecular assembly. Compounds 1 and 2 both show remarkable ligand-enhanced photo-induced color-changing behavior, with their pink crystals immediately turning to yellow crystals under UV light illumination.

Dynamic Adaptive Two-Dimensional Supramolecular Assemblies for On-Demand Filtration.

SummaryThe construction of synthetic two-dimensional (2D) materials designates a pathway to the versatile chemical functionality by spatial control. However, current 2D materials with intelligence of stimuli-responsibility and adaptiveness have been unfledged. The approach reported here uses a supramolecular strategy to achieve the dynamic non-covalent self-assembly of a rationally designed small molecule monomer, producing large-area, ultra-thin, porous 2D supramolecular assemblies, which are solution-processable in aqueous solution. Importantly, the 2D supramolecular assemblies exhibit distinct adaptive capability to automatically regulate their network density and pore diameters in response to environmental temperature change, which could be developed into an "on-demand" filtration application for nanoparticles. Meanwhile, the 2D supramolecular assemblies can also perform reversible degradation/reformation by photo-irradiation. Our results not only show the simplicity, reliability, and effectiveness of supramolecular strategies in the construction of 2D materials with practical sizes, but also push the dynamic alterability and adaptation features from supramolecular assemblies toward 2D materials.

Structural aspects, spectroscopic and third order nonlinear optical properties of mixed ligand complexes from NNO tridentate Schiff base: Crystal structure of a rare proton bridged Ni(II) complex

Three novel mixed ligand complexes of cadmium(II), zinc(II) and nickel(II), derived from the parent Schiff base 4-chloro-2-((2-(dimethylamino)ethylimino)methyl)phenol, were synthesized and characterized by means of single crystal XRD, elemental analysis, IR, electronic and NMR spectral studies. In all the three complexes either reactant amine or aldehyde coordinates to the metal centers along with Schiff base and nickel(II) complex is having a rare proton bridged structure. While complex 1 crystallizes in orthorhombic Pbca space group, both complexes 2 and 3 crystallize in triclinic P1‾ space group. Different types of intermolecular interactions present in the crystal systems paved way to form 1D and 2D supramolecular assemblies and the visual analysis of those intermolecular interactions was achieved through Hirshfeld surface analysis. All the three complexes exhibited a negative solvatochromic behavior. Photoluminescent studies were carried out and quenching of fluorescence was observed in all complexes which is supported by the quantum yield values. Third order NLO properties were investigated by Z-scan technique with 75 fs laser pulse at 800 nm. NLO responses of the complexes were controlled by nonlinear refractive processes which make them suitable candidates for optical switching applications.

Photo/redox-responsive 2D-Supramolecular assembly involving Cucurbit[8]uril and a star-shaped porphyrin tecton

Abstrac The present paper reports on the formation and on the electrochemical/spectroscopic characterization of inclusion complexes formed in aqueous media between cucurbit[7 or 8]urils cavitands (CB[7], CB[ 8 ]) and a rigid four-pointed star-shaped viologen-appended porphyrin tecton. The formation of discrete 4:1 pseudo-rotaxane-like caviplexes, involving threading of CB[n] rings on the rigid viologen-based star's branches has been demonstrated by nuclear magnetic resonance and mass spectrometry measurements. Then, the photo- and redox-triggered formation of 2D supramolecular assemblies involving CB[8]s and the four electron reduced tectons as key building elements, has been established on the ground of in-depth electrochemical and spectroscopic analyses supported by quantum calculations. The CB[8]-promoted intermolecular π-dimerization of the viologen cation radicals introduced at the meso positions of the porphyrin plateform has been brought to light through the diagnostic signatures of the 1:2 host-guest ternary caviplexes formed between viologen and CB[8] and by spectroscopic data collected after electrochemical, chemical or photochemical reduction of the viologen-based tectons. The CB[8] hosts not only proved useful to promote the redox-triggered formation of supramolecular assemblies, it was also found to prevent the chemical reduction of the porphyrin ring in aqueous media and its subsequent conversion into phlorin products.

Orthogonal Halogen‐Bonding‐Driven 3D Supramolecular Assembly of Right‐Handed Synthetic Helical Peptides

AbstractPeptide‐mediated self‐assembly is a prevalent method for creating highly ordered supramolecular architectures. Herein, we report the first example of orthogonal C−X⋅⋅⋅X−C/C−X⋅⋅⋅π halogen bonding and hydrogen bonding driven crystalline architectures based on synthetic helical peptides bearing hybrids of l‐sulfono‐γ‐AApeptides and natural amino acids. The combination of halogen bonding, intra‐/intermolecular hydrogen bonding, and intermolecular hydrophobic interactions enabled novel 3D supramolecular assembly. The orthogonal halogen bonding in the supramolecular architecture exerts a novel mechanism for the self‐assembly of synthetic peptide foldamers and gives new insights into molecular recognition, supramolecular design, and rational design of biomimetic structures.

One-, Two-, and Three-Dimensional Supramolecular Assemblies Based on Tubular and Regular Polygonal Structures of Pillar[ n ]arenes

Pillar[ n]arenes, which were first reported by our group in 2008, are promising macrocyclic compounds in supramolecular chemistry. The simple, tubular, and highly symmetrical shape of pillar[ n]arenes has allowed various supramolecular assemblies with well-defined structures to be constructed. The pillar-shaped structures of pillar[ n]arenes are suitable for surface modification and formation of one-dimensional (1D) channels. The regular polygonal prism shape of organized pillar[ n]arenes contributes to the construction of highly assembled structures such as two-dimensional (2D) sheets and three-dimensional (3D) spheres. In this minireview, we describe supramolecular assemblies with various dimensions. First, we discuss 1D supramolecular assemblies based on tubular structures of pillar[ n]arenes. Second, 2D supramolecular sheet formation based on regular polygonal structures is described. Finally, 3D supramolecular assemblies such as vesicles and 3D frameworks constructed from pillar[ n]arenes are discussed.

Photoreaction-driven two-dimensional periodic polyrotaxane-type supramolecular nanoarchitecture.

A 2D polypseudorotaxane-type assembly was constructed using cucurbit[8]uril and styrylpyridinium-bearing triphenylamine. In addition, tunable non-covalent to covalent transition was achieved by [2+2] photodimerization of styrylpyridinium units. Thus, a more stable 2D polyrotaxane-type nanoarchitecture was obtained, which could capture [60]fullerene and further exhibit an excellent photodynamic therapy effect.

A Co(II)-Hydrazone Schiff Base Single Ion Magnet Exhibiting Field Induced Slow Relaxation Dynamics

An octahedral Co(II) complex with N′-(2-hydroxybenzylidene)acetohydrazide Schiff base ligand [HL] forms a 3D supramolecular assembly supported by non-coordinating ClO4− ions and H2O molecules. Individual spin centres are non-interacting and give rise to significant spin-orbit coupling, resulting in field induced slow magnetisation relaxation; which is characteristic of Single Ion Magnet (SIM) behaviour.

Noncovalent-bonded 2D–3D Zn2+, Cd2+, and Cu2+ supramolecular coordination complexes with 2,2′-bipyridine and carboxylates: their synthesis and characterization

The present report pertains to the synthesis and characterization of six mixed-ligand complexes of [Zn(L)(pip-)2] (1) (L = 2,2′-bipyridine, pip =1,3-benzodioxole-5-carboxylate), [Zn(L)(mpp–)2·H2O]·H2O (2) (mpp =2-methyl-2-phenoxypropanoate), [Cu(L)(mca–)2]·5H2O (3) (mca = p-methoxycinnamate), [Cd(L)( mca–)2·2H2O] (4), [Cd(L)2(mpp–)2]·H2O (5) and [Cu(L)(pdp2-)0.5Cl·H2O]2·8H2O (6) (pdp =1,4-piperazinedipropionate). The resulting complexes were characterized from EA, IR, and single-crystal XRD analysis. The TGA of all complexes were also evaluated. Compound 2 is a 2D sheet; all other complexes are 3D supramolecular assemblies. Zn and Cd have octahedral coordination geometry and Cu tetrahedral or square-pyramidal coordination.The single-crystal XRD studies showed that 1–5 are mononuclear, while 6 is a centrosymmetric dinuclear complex. The 2,2′-bipyridines are chelating bidentate to the metal ions. The COO– is monodentate in 2–6, while COO– in 1 has chelating bidentate coordination. The pyridine 3(3′)-CH participated in the CH–O contact in each compound. The intricate intra- and intermolecular classical H-bonds, CH–Cl, C–H···O, CH2···O, CH3···O, O···π, C–π, C–H···π, CH3–π, and π–π associations are elucidated from the X-ray crystallographic studies bringing the discrete complexes into high-dimensional ordered supramolecular structures.

A 3D supramolecular assembly of Co(II) MOF constructed with 2,5-pyridinedicarboxylate strut and its catalytic activity towards synthesis of tetrahydrobiphenylene-1,3-dicarbonitriles

A cobalt based MOF, [Co(2,5-Pydc)(H2O)2].H2O (CoPy) was hydrothermally synthesized by employing 2,5-Pyridinedicarboxylic acid (2,5-Pydc) as organic strut; and its characteristics were characterized by single crystal XRD, FT-IR, TGA and fluorescent measurements. The single crystal XRD studies reveals that the compound crystallized in orthorhombic crystal system of space group P212121 with lattice parameters a = 7.3253(1) Å b = 9.3906(1) Å c = 13.8054(2) Å. In CoPy, the central metal atom (Co2+) adopts a six coordination geometry by using the carboxylate oxygen atoms and nitrogen atom of pyridine ring of 2,5-Pydc. The compound is linked with 2,5-Pydc ligand in all three directions through hydrogen bonding and π-π stacking interactions, which further develops a supramolecular 3-dimensional assembled network. The CoPy exhibited impressive catalytic activity in the synthesis of seven tetrahydrobiphenylene-1,3-dicarbonitrile derivatives via an one-pot, three-component reaction between aromatic aldehyde, malononitrile and 3-methyl-cyclohexanon in ethanol giving excellent yields (91–96%) in 20-35 min reaction time. The Lewis acidic sites of CoPy, by Co2+ open metal sites probably ensure its catalytic performance. The eco-friendly protocol and recyclability of CoPy, with no noticeable leaching of metal ion, undoubtedly makes it an ideal catalyst.

Synthesis, spectral characterization and structural studies of a novel O, N, O donor semicarbazone and its binuclear copper complex with hydrogen bond stabilized lattice

A novel O,N,O donor salicylaldehyde–N4–phenylsemicarbazone, (H2L) has been synthesized and physicochemically characterized. Detailed structural studies of H2L using single crystal X–ray diffraction technique reveals the existence of intra and inter molecular hydrogen bonding interactions, which provide extra stability to the molecule. We have successfully synthesized a binuclear copper(II) complex, [Cu2(HL)2(NO3)(H2O)2]NO3 with phenoxy bridging between the two copper centers. The complex was characterized by elemental analysis, magnetic susceptibility and conductivity measurements, FT–IR, UV–Visible, mass and EPR spectral methods. The grown crystals of the copper complex were employed for the single crystal X–ray diffraction studies. The complex possesses geometrically different metal centers, in which the ligand coordinates through ketoamide oxygen, azomethine nitrogen and deprotonated phenoxy oxygen. The extensive intermolecular hydrogen bonding interactions of the coordinated and the lattice nitrate groups interconnect the complex units to form a 2D supramolecular assembly. The ESI mass spectrum substantiates the existence of 1:1 complex. The g values obtained from the EPR spectrum in frozen DMF suggest dx2−y2 ground state for the unpaired electron.

Structure Formation in 2D Assemblies Comprising Functional Tripod Molecules with Reduced Symmetry

Surface-confined self-assembly of organic building blocks is a versatile method of creation of low dimensional structures with potential applications in nanotechnology and material engineering. A key factor which often determines morphology of such 2D supramolecular assemblies is the geometry and functionality of a molecular tecton at play. In this contribution, we use theoretical modeling to predict the structure of adsorbed systems in which tripod molecules with reduced symmetry interact via a short-range anisotropic pair potential. To that end the self-assembly of a tripod molecule with one shortened/elongated arm, adsorbed on a triangular lattice, is modeled using the Monte Carlo simulation method. The probe asymmetric molecule consists of a few interconnected segments, and it is equipped with terminal interaction centers (active segments) with differently assigned interaction directions. Our study focuses on the effect of directionality of intermolecular interactions on the morphology of the resulting supramolecular 2D assemblies. It is demonstrated that a suitable encoding of the interaction directions allows for the creation of largely diversified adsorbed structures including aperiodic porous networks, molecular ladders, strings, ribbons and dispersed aggregates. Main differences and similarities between the findings reported for the asymmetric molecules and their C3-symmetric counterparts are also discussed. The obtained results can be helpful in designing new molecular tectons for controlled on-surface self-assembly and coupling reactions, as they provide useful information on the molecule–superstructure relation. This preliminary information can, for example, facilitate screening of molecular libraries to select an optimal molecule able to create low-dimensional structures with predefined properties.