Supramolecular Coordination Complexes Research Articles

Highly robust supramolecular polymer networks crosslinked by a tiny amount of metallacycles

Supramolecular polymeric materials have exhibited attractive features such as self-healing, reversibility, and stimuli-responsiveness. However, on account of the weak bonding nature of most noncovalent interactions, it remains a great challenge to construct supramolecular polymeric materials with high robustness. Moreover, high usage of supramolecular units is usually necessary to promote the formation of robust supramolecular polymeric materials, which restrains their applications. Herein, we describe the construction of highly robust supramolecular polymer networks by using only a tiny amount of metallacycles as the supramolecular crosslinkers. A norbornene ring-opening metathesis copolymer with a 120° dipyridine ligand is prepared and self-assembled with a 60° or 120° Pt(II) acceptor to fabricate the metallacycle-crosslinked polymer networks. With only 0.28 mol% or less pendant dipyridine units to form the metallacycle crosslinkers, the mechanical properties of the polymers are significantly enhanced. The tensile strengths, Young’s moduli, and toughness of the reinforced polymers reach up to more than 20 MPa, 600 MPa, and 150 MJ/m3, respectively. Controllable destruction and reconstruction of the metallacycle-crosslinked polymer networks are further demonstrated by the sequential addition of tetrabutylammonium bromide and silver triflate, indicative of good stimuli-responsiveness of the networks. These remarkable performances are attributed to the thermodynamically stable, but dynamic metallacycle-based supramolecular coordination complexes that offer strong linkages with good adaptive characteristics.

Supramolecular Coordination Complexes for Synergistic Cancer Therapy.

ConspectusSupramolecular coordination complexes (SCCs) are predictable and size-tunable supramolecular self-assemblies constructed through directional coordination bonds between readily available organic ligands and metallic receptors. Based on planar and 3D structures, SCCs can be mainly divided into two categories: metallacycles (e.g., rhomboidal, triangular, rectangular, and hexagonal) and metallacages (e.g., tetrahedral, hexahedral, and dodecahedral). The directional coordination bonds enable the efficient formation of metallacycles and metallacages with well-defined architectures and geometries. SCCs exhibit several advantages, including good directionality, strong interaction force, tunable modularity, and good solution processability, making them highly attractive for biomedical applications, especially in cellular imaging and cancer therapy. Compared with their molecular precursors, SCCs demonstrate enhanced cellular uptake and a strengthened tumor accumulation effect, owing to their inherently charged structures. These properties and the chemotherapeutic potential inherent to organic platinum complexes have promoted their widespread application in antitumor therapy. Furthermore, the defined structures of SCCs, achieved via the design modification of assembly elements and introduction of different functional groups, enable them to combat malignant tumors through multipronged treatment modalities. Because the development of cancer-treatment methodologies integrated in clinics has evolved from single-modality chemotherapy to synergistic multimodal therapy, the development of functional SCCs for synergistic cancer therapy is crucial. While some pioneering reviews have explored the bioapplications of SCCs, often categorized by a specific function or focusing on the specific metal or ligand types, a comprehensive exploration of their synergistic multifunctionality is a critical gap in the current literature.In this Account, we focus on platinum-based SCCs and their applications in cancer therapy. While other metals, such as Pd-, Rh-, Ru-, and Ir-based SCCs, have been explored for cancer therapy by Therrien and Casini et al., platinum-based SCCs have garnered significant interest, owing to their unique advantages in antitumor therapy. These platinum-based SCCs, which enhance antitumor efficacy, are considered prominent candidates for cancer therapies owing to their desirable properties, such as potent antitumor activity, exceptionally low systemic toxicity, active tumor-targeting ability, and enhanced cellular uptake. Furthermore, diverse diagnostic and therapeutic modalities (e.g., chemotherapy, photothermal therapy, and photodynamic therapy) can be integrated into a single platform based on platinum-based SCCs for cancer therapy. Consequently, herein, we summarize our recent research on platinum-based SCCs for synergistic cancer therapy with particular emphasis on the cooperative interplay between different therapeutic methods. In the Conclusions section, we present the key advancements achieved on the basis of our research findings and propose future directions that may significantly impact the field.

Pt(II)/Pd(II)-Based Metallosupramolecular Architectures as Light Harvesting Systems and their Applications.

The development of artificial light-harvesting systems mimicking the natural photosynthesis method is an ever-growing field of research. Numerous systems such as polymers, metal complexes, POFs, COFs, supramolecular frameworks etc. have been fabricated to accomplish more efficient energy transfer and storage. Among them, the supramolecular coordination complexes (SCCs) formed by non-covalent metal-ligand interaction, have shown the capacity to not only undergo single and multistep energy migration but also to utilize the harvested energy for a wide variety of applications such as photocatalysis, tunable emissive systems, encrypted anti-counterfeiting materials, white light emitters etc. This review sheds light on the light-harvesting behavior of both the 2D metallacycles and 3D metallacages where design ingenuity has been executed to afford energy harvesting by both donor ligands as well as metal acceptors.

Pt(II)/Pd(II)‐Based Metallosupramolecular Architectures as Light Harvesting Systems and their Applications

AbstractThe development of artificial light‐harvesting systems mimicking the natural photosynthesis method is an ever‐growing field of research. Numerous systems such as polymers, metal complexes, POFs, COFs, supramolecular frameworks etc. have been fabricated to accomplish more efficient energy transfer and storage. Among them, the supramolecular coordination complexes (SCCs) formed by non‐covalent metal‐ligand interaction, have shown the capacity to not only undergo single and multistep energy migration but also to utilize the harvested energy for a wide variety of applications such as photocatalysis, tunable emissive systems, encrypted anti‐counterfeiting materials, white light emitters etc. This review sheds light on the light‐harvesting behavior of both the 2D metallacycles and 3D metallacages where design ingenuity has been executed to afford energy harvesting by both donor ligands as well as metal acceptors.

Covalent Post-Synthetic Modification of Metal-Organic Cages: Concepts and Recent Progress.

Metal-organic cages (MOCs) are supramolecular coordination complexes that have internal cavities for hosting guest molecules and exhibiting various properties. However, the functions of MOCs are limited by the choice of the building blocks. Post-synthetic modification (PSM) is a technique that can introduce new functional groups and replace existing ones on the MOCs without changing their geometry. Among many PSM methods, covalent PSM is a promising approach to modify MOCs with tailored structures and functions. Covalent PSM can be applied to either the internal cavity or the external surface of the MOCs, depending on the functionality expected to be customized. However, there are still some challenges and limitations in the field of covalent PSM of MOCs, such as the balance between the stability of MOCs and the harshness of organic reactions involved in covalent PSMs. This concept article introduces the organic reaction types involved in covalent PSM of MOCs, their new applications after modification, and summarizes and provides an outlook of this research field.

Recent advances in combatting bacterial infections via well-designed metallacycles/metallacages.

Bacterial infections can lead to the development of large-scale outbreaks of diseases that pose a serious threat to human life and health. Also, conventional antibiotics are prone to producing resistance and allergic reactions, and their therapeutic effect is dramatically diminished when bacterial communities form biofilms. Fortunately, well-designed supramolecular coordination complexes (SCCs) have been used as antibacterials or anti-biofilms in recent years. SCCs can kill bacteria by directly engaging with the bacterial surface through electrostatic interactions or by penetrating the bacterial membrane through the auxiliary effect of cell-penetrating peptides. Furthermore, scientists have engineered fluorescent SCCs that can produce reactive oxygen species (ROS) to eliminate bacteria when exposed to laser irradiation, and they also demonstrate outstanding performance in in vivo imaging, enabling integrated diagnosis and treatment. In this review, we summarize the design strategy and applications of SCCs in antibacterials or anti-biofilms and provide an outlook on future research.

Strategies to address key challenges of metallacycle/metallacage-based supramolecular coordination complexes in biomedical applications.

Owing to their capacity for dynamically linking two or more functional molecules, supramolecular coordination complexes (SCCs), exemplified by two-dimensional (2D) metallacycles and three-dimensional (3D) metallacages, have gained increasing significance in biomedical applications. However, their inherent hydrophobicity and self-assembly driven by heavy metal ions present common challenges in their applications. These challenges can be overcome by enhancing the aqueous solubility and in vivo circulation stability of SCCs, alongside minimizing their side effects during treatment. Addressing these challenges is crucial for advancing the fundamental research of SCCs and their subsequent clinical translation. In this review, drawing on extensive contemporary research, we offer a thorough and systematic analysis of the strategies employed by SCCs to surmount these prevalent yet pivotal obstacles. Additionally, we explore further potential challenges and prospects for the broader application of SCCs in the biomedical field.

Tetracosanuclear nickel complexes as effective catalysts for cycloaddition of carbon dioxide with epoxides.

A series of well-defined tetracosanuclear nickel complexes 3-7 facilely produced by one-pot synthesis were active catalysts for cycloaddition of CO2 and cyclohexene oxide (CHO). These nickel complexes were doughnut-like supramolecular coordination complexes involving eight repeating units, and each of them contains one Schiff base ligand and three nickel(II) ions. Notably, the 24-nuclear nickel cluster complex 3 in combination with nucleophilic additives was the most efficient catalyst to mediate CO2 coupling with CHO to generate CO2-based cis-cyclohexene carbonates. In addition to CO2/CHO cycloaddition, complex 3 was also found to effectively couple CO2 with other alicyclic epoxides, generating the corresponding cyclic carbonates. Additionally, kinetic investigations for CO2 cycloaddition of CHO using 3 were reported.

Dual-Emissive Rectangular Supramolecular Pt(II)-p-Biphenyl with 4,4'-Bipyridine Derivative Metallacycles: Stepwise Synthesis and Photophysical Properties.

Mixed-ligand tetranuclear supramolecular coordination complexes (SCCs) of Pt(II)-p-biphenyl and bridging ligands derivatives of 4,4'-bypiridine (8)-(10), were synthesized and characterized. The SCCs were synthesized stepwise, starting from the Pt-p-biphenyl -Pt core. The crystal structure of complex {[Pt(2,2'-bpy)]4(μ-bph)2(μ-(4,4'-bpy)2}{PF6}4 (2,2'-bpy = 2,2'-bipyridine, bph = p-biphenyl and 4,4'-bpy = 4,4' bipyridine), was determined using single-crystal diffraction methods. The emission profile of the tetranuclear complexes (8)-(10) was influenced by the length of the bridging ligands and was found to depend on solvent polarity. Dual-emission patterns in methanol-water mixtures were observed only in the cases of complexes (9) and (10), attributed to aggregation-induced emission phenomena.

Reversible and Turn-On Fluorescence Detection of Phosphate in Aqueous Solution and Living Cell Imaging by Supramolecular Metallacycles with AIE-Active Ligands.

Luminescent supramolecular metallacycles have attracted great interest as a new promising class of sensing substrates. In this work, two tetraphenylethene (TPE)-based diimidazole and dipyrazole ligands with the aggregation-induced emission (AIE) feature were designed for the construction of supramolecular tetragonal metallacycles 1-4 with two 90° mononuclear [(bpy)M]2+ or dinuclear [(bpy)2M2]4+ acceptors (bpy = 2,2'-dipyridine; M = Pd, Pt), in which the fluorescence can be quenched to an "off" state due to the ligand-to-metal charge transfer (LMCT). Metallacycle 1 was utilized as a fluorescence sensor for phosphate (PO43-) detection in aqueous solution by means of disassembly, leading to the release of the ligand. Additionally, the metallacycle can be regenerated through self-assembly via the introduction of Pd(II) acceptors. PO43- was detected using TPE-based metallacycles over a wide concentration range, with a detection limit as low as 2.1 × 10-8 M. Furthermore, sensor 1 also presented the semiquantitative visual detection ability for PO43- in the test paper mode via fluorescence changes. The aforementioned studies not only enhance the current research on fluorescent materials but also offer a strategy for the creation of stimuli-responsive supramolecular coordination complexes.

Synthesis of 177Lu-Labeled, Somatostatin-2 Receptor-Targeted Metalla-Assemblies: Challenges in the Design of Supramolecular Radiotherapeutics.

Self-assembled supramolecular coordination complexes (SCCs) hold promise for biomedical applications in cancer therapy, although their potential in the field of nuclear medicine is still substantially unexplored. Therefore, in this study an exo-functionalized cationic [Pd2L2]4+ metallacycle (L = 3,5-bis(3-ethynylpyridine)phenyl), targeted to the somatostatin-2 receptor (sst2R) and featuring the DOTA chelator (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) in order to bind the β-- and γ-emitter lutetium-177, was synthesized by self-assembly following ligand synthesis via standard solid-phase peptide synthesis (SPPS). This metallacycle was then characterized by reverse-phase high-performance liquid chromatography (RP-HPLC), electrospray ionization mass spectrometry (ESI-MS), and 1H and 1H-DOSY NMR (DOSY = diffusion-ordered spectroscopy). A procedure for the radiolabeling of the metallacycle with 177Lu was also optimized. The resulting [nat/177Lu]Lu-DOTA-metallacycle, termed [nat/177Lu]Lu-Cy, was evaluated concerning its stability and in vitro properties. The compound was more lipophilic compared to the reference [177Lu]Lu-DOTA-TATE (logPOct/H2O = -0.85 ± 0.10 versus -3.67 ± 0.04, respectively). While [natLu]Lu-Cy revealed low stability in a DMEM/F12 GlutaMax medium, it demonstrated good stability in other aqueous media as well as in DMSO. A high sst2R binding affinity (expressed as IC50) was determined in CHOsst2 cells (Chinese hamster ovary cells that were stably transfected with human sst2R). Moreover, the metallacycle exhibited high human serum albumin binding, as assessed by high-performance affinity chromatography (HPAC), and moderate stability in human serum compared to [177Lu]Lu-DOTA-TATE (TATE = (Tyr3)-octreotate). In order to improve stability, a heteroleptic approach was used to develop a less sterically hindered cage-like SCC that is potentially endowed with host-guest chemistry capability, which has been preliminarily characterized by RP-HPLC and ESI-MS. Overall, our initial results encourage future studies on sst2R-directed SCCs and have led to new insights into the chemistry of ss2R-directed SCCs for radiopharmaceutical applications.

Self-Assembly of Rhenium(I) Double-Stranded Helicate and Mesocate from Flexible Ditopic Benzimidazolyl/Naphthanoimidazolyl N-Donor and Rigid Bis-Chelating Hydroxyphenylbenzimidazolyl N∩OH-Donor Ligands: Synthesis, Characterization, and Photophysical and B-DNA Docking Studies.

The self-assembly of three rheniumtricarbonyl core-based supramolecular coordination complexes (SCCs), fac-[Re(CO)3(μ-L)(μ-L')Re(CO)3] (1-3) was carried out using Re2(CO)10, rigid bis-chelating ligand (HO∩N-Ph-N∩OH (L1) (where HO∩N = 2-hydroxyphenylbenzimidazolyl), and flexible ditopic N-donor ligands (L2 = bis(3-((1H-benzoimidazol-1-yl)methyl)-2,4,6-trimethylphenyl)methane, L3 = bis(3-((1H-naphtho[2,3-d]imidazol-1-yl)methyl)-2,4,6-trimethylphenyl)methane, L4 = bis(4-(naphtho[2,3-d]imidazol-1-yl-methyl)phenyl)methane) via a one-pot solvothermal approach. In the solid state, the dinuclear SCCs adopt heteroleptic double-stranded helicate and meso-helicate architectures. The supramolecular structures of the complexes are retained in the solution based on the 1H NMR and electrospray ionization (ESI)-mass analysis. The spectral and photophysical properties of the complexes were studied both experimentally and using time-dependent density functional theory (TDDFT) calculations. All of the supramolecules exhibited emission in both solution and solid states. Theoretical studies were conducted to determine the chemical reactivity parameters, molecular electrostatic potential surface plots, natural population, and Hirshfeld analysis for complexes 1-3. Additionally, molecular docking studies were carried out for complexes 1-3 with B-DNA.

Quinolyl-Based PGM Metallarectangles: Antiproliferative Activity, DNA and BSA Protein Interactions, and a Molecular Docking Perspective.

The increased success of small metal-containing molecules as pharmaceutical agents has prompted investigations into the pharmacological activity of a different class of metal-based compounds; supramolecular coordination complexes (SCCs). Such complexes have been extensively investigated for their anticancer activity, with many displaying activities comparable or superior to available clinical chemotherapeutic drugs. Here, we evaluated a series of quinoline-containing binuclear complexes and metallarectangles for their in vitro anticancer activity in the hormone receptor positive MCF-7 and triple negative MDA-MB-231 breast cancer cell lines. The preliminary cytotoxic screen, in the MCF-7 cell line, revealed that the ligand (7-chloro-4-(pyridin-4-yl)quinoline, L) and metallarectangle [{Ir(μ-Cl)(Cp*)}4 (μ-L)2 ](OTf)4 display superior activity to cisplatin, while [{Ru(p-cymene)}4 (μ-η2 -η2 -C2 O4 )2 (μ-L)2 ](OTf)4 was more potent than cisplatin in the triple-negative MDA-MD-231 cell line. Upon evaluation in a multidose screen, ligand L and metallarectangle [{Ir(μ-Cl)(Cp*)}4 (μ-L)2 ](OTf)4 displayed antiproliferative activity almost two-fold greater than cisplatin in the MCF-7 cell line, while [{Ru(p-cymene)}4 (μ-η2 -η2 -C2 O4 )2 (μ-L)2 ](OTf)4 was over two-times more active than cisplatin in the MDA-MB-231 cell line. Additionally, using the non-tumorigenic MCF-12 A breast epithelial cell line, the compounds demonstrate increased selectivity toward breast cancer cells over non-tumorigenic cells. Furthermore, investigations into the interactions of ligand L and selected complexes with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) indicate favourable binding.

Organometallic-Organic Hybrid Assemblies Featuring the Diantimony Complex [Cp2Mo2(CO)4(μ,η2-Sb2)], Ag(I) Ions and Ndonor Molecules as Building Blocks.

The reactions of the of the organometallic ligand complex [Cp2Mo2(CO)4(μ,η2-Sb2)] (C) with Ag[TEF] ([TEF]‾ = [Al{OC(CF3)3}4]‾) in the presence of a number of di- or polytopic N-donor molecules (1,6,7,12-tetraazaperylene (L1), 2,2'-bipyrimidine (L2), 4,4'-bipyridine (L3), trans-1,2-di(4-pyridyl)ethylene (L4)) and 1,3-di(4-pyridyl)propane (L5), were studied. These reactions lead, depending on the reaction stoichiometry and choice of linker, to the selective formation of dimeric or tetrameric supramolecular coordination complexes as well as 1D and 2D coordination polymers (CPs). The presented compounds are unique examples of supramolecular complexes incorporating both organometallic Sb-donor and organic N-donor molecules as ligands to stabilize metal ions. Moreover, one of the formed compounds, the CP [Ag4(η2:1-C)4(L4)4]n[TEF]4n, represents an exceptional 1D polymer incorporating both N- and Sb-donor ligands as connectors for metal ions.

High-internal phase Pickering emulsion stabilized by crystals of nobiletin: assembly of supramolecular metal-polyphenolic coordination complexes for surface coating.

High internal phase Pickering emulsion has attracted extensive attention due to its unique properties, and has broad application prospects in the food field, such as as a fat replacer, packaging and delivery of nutrients or probiotics, and 3D printing of food. However, efficient and edible high-internal phase Pickering stabilizer is still a persistent challenge for food scientists. Herein, the nobiletin (NOB) was selected as a model substance, the particle physicochemical properties (droplet size, rheological behavior, and transmission profile) showed that supramolecular metal-polyphenolic coordination networks could suppress the ripening and growth of crystals on the oil-water interface. When the ratio of tannic acid (TA) and Fe3+ was 3:1, the crystallization growth of NOB could be effectively inhibited. Due to the reduction of energy steric hindrance in the adsorption process, the resulting NOB-TA3 -Fe3+ 1 (NT3 Fe1 ) nanoparticles had the greatest potential to extend emulsion storage time. This particle could stabilise a high-internal phase emulsion, of which the oil phase was 80%, for at least 30 days and eventually lead to high system viscosity. The findings in this work provided a novel selection of healthy emulsifiers as well as an effective emulsion delivery system for hydrophobic and crystalline nutrients. This article is protected by copyright. All rights reserved.

Topological effect on fluorescence emission of tetraphenylethylene-based metallacages

Herein, we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks. Specifically, the tetraphenylethylene-based donor and two acceptors with different numbers of Pt(II) centers were combined via coordination-driven self-assembly. Owing to the differences in the shapes of the assemblies, the resultant ball-shaped metallacage displayed stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions, while a reversal of fluorescence intensities was observed in the aggregation process. Overall, this work demonstrates that the photophysical properties of supramolecular coordination complexes can be affected by subtle geometrical factors, which can be controlled precisely at the molecular level.

9,10-Bis(diphenylmethylene)-9,10-dihydroanthracene-based metal-organic assemblies with aggregation-induced emission for multiple sensing

Developing novel emissive supramolecular assemblies with elegant architectures and tunable performance remains highly desirable yet challenging. Herein, we report the design and synthesis of several 9,10-bis(diphenylmethylene)-9,10-dihydroanthracene-based metal-organic assembles with aggregation-induced emission characteristics. Such assemblies feature intriguing thermochromic and mechanochromic properties, i.e., distinguishable fluorescence responses in terms of emission wavelength and intensity under variable temperatures and pressures. Moreover, these assemblies can serve as excellent fluorescent sensors for the detection of polysaccharide molecules. Due to the differentiated charge type and density, the assembles display distinct sensing mechanisms toward different polysaccharide molecules. This study provides novel perspectives for the synthesis of butterfly-like platinum(II) supramolecular coordination complexes with multistimuli-responsiveness for polysaccharide sensing, which will facilitate the development of stimuli-responsive materials

Trefoil-shaped metallacycle and metallacage via heteroleptic self-assembly

Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional (2D) and three-dimensional (3D) supramolecules, but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge. Here we report two discrete trefoil-shaped metallacycle S1 and metallacage S2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands. The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic ‘Mitsubishi’ motif. The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2. The formed metallacage S2 possesses a molecular weight up to 36 kDa, diameter 6.6 nm and height 3.0 nm. All supramolecular coordination complexes were fully characterized by NMR spectroscopy (1H NMR, 2D COSY, 2D NOESY, 2D DOSY), high-resolution electrospray ionization mass spectrometry ESI-MS, ESI-TWIM-MS, TEM and AFM.

Self-Sorting of Transient Polymer Networks by the Selective Formation of Heteroleptic Metal–Ligand Complexes

Advances in self-sorting mechanisms have resulted in the development of a broad library of well-defined supramolecular coordination complexes (SCCs) with unprecedented geometries. These SCCs have promising applications like those in catalysis and solar cells. Moreover, the dynamic nature of coordination bonds allows them to undergo stimuli-responsive topology rearrangements, which are used in a plethora of molecular machines. These advances are, however, rarely employed in the design of metallo-supramolecular polymer networks (MSPNs). To address this gap, we use steric hindrance as a powerful self-sorting mechanism to construct MSPNs based on the selective formation of heteroleptic complexes. We graft tetra-arm poly(ethylene glycol) precursors with sterically demanding 2,9-bis(mesitylene)-1,10-phenanthroline or two slim unsubstituted phenanthroline and terpyridine ligands and study their complexation-induced gel formation. Rheological data disclose that the heteroleptic complexation, which is controlled by the coordination geometry preference of the utilized metal ion, can induce up to 5 orders of magnitude delay in the network relaxation and more than twofold increase in plateau modulus due to the removal of primary loops. The structural/electronic characterization of complexes by density functional theory nicely explains the distinct performance of different metal ions in gel formation. These results open a promising interface between polymer science and coordination chemistry that can ultimately lead to the development of new hybrid materials with exceptional properties and novel stimuli responsiveness.

The investigation of modification in structural flexibility and coordination modes in a solvent free β-diketone Cu(II) complex by crystal structure and DFT studies

Coordination-driven self-assembly in inorganic complexes is a viable methodology to construct supramolecular coordination complexes. Crystal engineering of β-diketone Cu(II) coordination complexes can be achieved via the host–guest complexation method. The effect of metal–ligand interactions (coordination polyhedra) on the supramolecular framework has been analysed by crystal structure and computational studies. A new crystal form of a Cu(II) complex with 4,4,4-trifluoro-naphthyl butanedione has been identified and characterized using various spectroscopic techniques. X-ray diffraction studies unveiled that complex 1, [Cu(TFNB)2], crystallized in the monoclinic (P21/n) space group and its solvent-induced crystal forms, complex 2, [Cu(TFNB)2DMSO] (Database Identifier: IVAKIC), and complex 3, [Cu(TFNB)2DMF] (Database Identifier: ZOCHOR), which were reported earlier, are in the triclinic (P1¯) crystal system. The previously reported crystal forms (complexes 2 and 3) are examples of a single crystal coordinated solvent exchange (SCCSE) transformation. In complex 1, the β-diketone molecules are attached to the metal ion in an equatorial form with a perfect square planar geometry, whilst complexes 2 and 3 feature a slightly distorted square pyramidal geometry with chelated donor oxygen atoms of the β-diketone ligands in equatorial sites and the crystallizing DMSO and DMF solvents are apically coordinated to the metal centre, respectively. Interestingly, the oxygen donors of the β-diketone ligands in complex 1 are inclined in a trans configuration, whereas in the solvent-induced pseudopolymorphic forms of complexes 2 and 3, a cis configuration is observed. The variation in the supramolecular framework with the coordination geometry in different crystal forms is analysed using the crystal structures and compared with quantum computational (Hirshfeld surface, enrichment ratio, energy framework, NCI index model and DFT) results. Molecular docking analysis was performed for all the complexes against the SARS-CoV2 main protease to explore the structure–property relationship.