Competition and Cooperation among Different Attractive Forces in

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The Competition and Cooperation among Different Attractive Forces in the Solutions of Inorganic-Organic Hybrids Containing Macroionic Clusters Jiancheng Luo, and Tianbo Liu Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.9b00480 • Publication Date (Web): 22 May 2019 Downloaded from http://pubs.acs.org on May 30, 2019

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The Competition and Cooperation among Different Attractive Forces in the Solutions of InorganicOrganic Hybrids Containing Macroionic Clusters Jiancheng Luo and Tianbo Liu* Department of Polymer Science, The University of Akron, Akron, Ohio 44325, USA KEYWORDS: Inorganic-organic hybrids, Macroion, Self-assembly, Stimuli-responsive behavior.

ABSTRACT: The hybrids composed of nanoscale inorganic clusters and organic ligands present as ideal models for understanding the different attractive forces during the self-assembly processes of complex macromolecules in solution. The counterion-mediated attraction induced by electrostatic interaction from the large, hydrophilic macroionic clusters can compete or cooperate with other types of attractive forces such as hydrophobic interaction, hydrogen bonding, π-π stacking and cation-π interaction from the organic ligands, consequently determining the solution behaviors of the hybrid molecules including their self-assembly process and the final supramolecular structures. The incorporation of organic ligands also leads to interesting responsive behaviors to external stimuli. Through the manipulation of hybrid composition, architecture, topology as well as solution conditions (e.g., solvent polarity, pH, and temperature), versatile selfassembled morphologies can be achieved, providing new scientific opportunities and potential applications.

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INTRODUCTION Understanding the roles and interplays of multiple non-covalent interactions in solution is important since they regulate the solution behaviors of numerous self-assembly and biophysical processes,1-7 but challenging as these forces have various interaction strengths, effective distances and different responses to the change of external conditions.8-11 The well-defined inorganicorganic hybrid macromolecules involving distinct moieties (e.g., hydrophilic and hydrophobic) and different types of interactions (e.g., electrostatic interaction, hydrogen bonding, hydrophobic interaction, and π-π stacking) are valuable models to understand such forces;12 on the other hand, the co-existence of multiple forces as well as the tunable relative strengths among them render hybrid molecules more fascinating solution behaviors compared to classic inorganic ions/clusters,13 surfactants,14-15 block copolymers16-17 and colloidal suspensions,18 with an important additional advantage of no or very small polydispersity. Several types of inorganic molecular clusters including polyoxometalates (POMs),19 polyhedral oligomeric silsesquioxane (POSS),20 fullerene (C60)21-22 and other small nanoparticles,23 have been broadly used as inorganic components to fabricate well-defined inorganic-organic hybrids, as summarized by a number of reviews.24-30 Consequently, these hybrids have been studied extensively in different states such as solution,12, 31-33 liquid crystalline,34-35 ionic liquids,36 bulk crystalline,37 surface and interface.38-40 In this feature article, we will present the solution studies with a series of inorganic-organic hybrids based on the charged inorganic molecular clusters (macroionic clusters) as shown in Figure 1. This article mainly covers the work from our group due to the requirement and the limited length, but it does not suggest that we ignore or undervalue the contributions from many other groups, or those work involving such hybrids in other areas beyond solution state.28, 41-48


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The fundamental logic we have applied for understanding these complex solution systems is summarized in Table 1. When various intermolecular forces (especially attractions, as the solvation, electrostatic repulsions and particles’ Brownian movements will keep molecules from aggregation/precipitation) co-exist in such hybrid solutions, it is essential to identify the major sources of attraction(s) under a given condition. These intermolecular forces include electrostatic interaction, cation-π interaction, hydrogen bonding, π-π stacking, van der Waals forces, hydrophobic interaction, etc.47-50 The cation-π interaction possesses electrostatic nature and therefore share the similarity to the electrostatic interaction. The van der Waals forces include dipole-dipole, dipole-induced dipole, and induced dipole-induced dipole interactions. Moreover, the hydrophobic interaction is a special type of van der Waals forces in solution. Due to the solvation effects in solution (especially water), the strength of hydrophobic interaction is much stronger compared to its strength in gas phase. The roles of different attractions can be evaluated by varying external conditions (e.g., solvent polarity, ionic strength, and temperature) because the relative strengths of various attractions will respond differently (Table 1),11,

49-52

which

accordingly will lead to the status changes of the hybrid molecules and result in different selfassembly behaviors, or the same type of assembly but different sizes and/or morphologies. The self-assembly

behaviors

are

usually

defined

as

“microphase

separations”

as

the

reorganization/association of molecules will minimize the total free energy, while the whole solution system is still thermodynamically stable.53-54 When the intermolecular attractions become even more dominant, the irreversible macrophase separation occurs as the solutes aggregate and eventually precipitate out from the solution.18, 55


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Table 1. The features of several attractive forces in macroionic solutions. Owing to the same nature, the electrostatic interaction and cation-π interaction have similar response to external conditions. The van der Waals forces and hydrophobic interaction also respond similarly. Upper/down arrows indicate stronger/weaker interactions due to the change of external conditions. The number of arrows shows the degree of response to external conditions. Strength (kcal/mol)

Effect Distance

Electrostatic Interaction

1 - 20

Long

Cation- Interaction

5 - 40

32 °C).102 As both Keggin clusters and PNIPAM chains are hydrophilic at low temperatures, the hybrid is not amphiphilic. Adding TBA+ salts into solution leads to the formation of single-layered blackberry-type structures due to the strong counterion-mediated attraction from TBA+ ions. If heating this solution, the scattered intensity from the solution and the assembly size undergo a significant change at above 40 °C, and the solution can be reverted to its original state with cooling, indicating that a reversible switch of self-assembled structures has been achieved (Figure 9b). At high temperatures, the nature of PNIPAM chains is switched from hydrophilic to hydrophobic, which changes the hybrids from hydrophilic to amphiphilic, and consequently triggers the transformation of self-assembled structures from single-layered blackberry structures to bilayer surfactant vesicles. MORPHOLOGICAL EVOLUTION OF SUPRAMOLECULAR STRUCTURES FORMED BY INORGANIC-ORGANIC HYBRIDS Different combinations of inorganic macroionic clusters and other molecules/clusters can be used to design hybrids with different molecular architecture, topology, volume fractions and surface functionality to enrich the variety of supramolecular morphology in hybrid systems. Compared to


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the well-studied surfactants/block copolymers, the hybrid molecules constructed by multiple inorganic clusters with shape persistence (“giant surfactants”) exhibit more complicated solution behaviors due to the arrangements of different cluster heads in self-assembled structures.28, 103-107 A series of amphiphilic hybrids are synthesized by Cheng’s group via connecting one or two POSS cages to the Keggin-type clusters (Figure 10a), and these hybrids show interesting selfassembly behaviors controlled by solvent polarity, molecular architecture, and crystallinity of the POSS cages.104 The dumbbell-shaped hybrids with one Keggin cluster and one BPOSS cage (functionalized with isobutyl groups, good crystallinity) can initially form spherical assemblies with internal lamellar structures in polar solvents, and the spherical assemblies are slowly transformed into 1D nanobelts upon aging, while only 3D stacked lamellae are observed in nonpolar solvents. The controlled studies show that the crystallinity of BPOSS cages is critical to the formation of these supramolecular structures. By replacing the crystallizable BPOSS cages to noncrystallizable CPOSS ones (functionalized with cyclohexyl groups, poor crystallinity), different morphologies including colloidal particles and 2D nanosheets are observed in polar solvents and non-polar solvents, respectively. When changing the molecular architecture by doubling the number of BPOSS cages (Keggin-2BPOSS), 2D nanosheets with the Keggin clusters facing outside are obtained. The formation of nanosheets requires the packing parameter close to 1, which can be significantly favored by considering the size of Keggin clusters and two BPOSS cages. Therefore, the 2D nanosheets formed by Keggin-2BPOSS show high stability in various solvents. When the number of BPOSS cages further increases, some distinct morphologies can be obtained. As demonstrated by Wang’s group, a wedged-shaped molecular architecture is achieved by linking one Dawson cluster and four BPOSS cages by a rigid organic linker (Dwason-4BPOSS in Figure 10b).105 In THF/water mixed solvents, honeycomb structures are observed under TEM studies.


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Interestingly, the combined images from high-magnification TEM, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and Fourier transform (FFT) pattern reveal that a well-ordered hexagonal symmetry (Figure 10b) like graphene has been formed in the honeycomb structures. The simulation shows that both counterion-mediated electrostatic interaction from the Dawson clusters and van der Waals interaction from the BPOSS cages are the major driving forces to determine the formation of graphene-like structures. Moreover, it also indicates that the specific wedged-shaped architecture plays a significant role by contributing directional entropic forces to stabilize the whole structures.

Figure 10. (a) Various self-assembled morphologies achieved by changing the solvent polarity, molecular architecture, and the functional groups on POSS cages in Keggin-POSS hybrid systems. Reprinted with permission from ref 104. Copyright 2016 American Chemical Society. (b)


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Structure of the Dawson-4BPOSS hybrid and schematic representation of its self-assembled graphene-like structures. Reprinted with permission from ref 105. Copyright 2018 American Chemical Society. The amphiphilic hybrids containing macroionic clusters can also present a good model to demonstrate the importance of packing parameter in determining different supramolecular morphologies, which is wildly reported in surfactant and block copolymer systems. Cheng and coworkers synthesized a PS-APOSS (hydrophilic, functionalized with -COOH groups) hybrid and observed interesting morphological transformation from vesicles to cylinders and spherical micelles (Figure 11a) in 1,4-dioxane, DMF, and DMF/NaOH, respectively.108 The Fouriertransform infrared spectroscopy (FTIR) measurements show that the ionization degree of -COOH groups is changed in various solvents, consequently leading to different strength of repulsive forces among the APOSS heads. To minimize the free energy, the APOSS heads are forced to adjust the distance between each other, which affects the surface area as well as the packing parameter, resulting into different supramolecular morphologies. Besides the degree of ionization of the -COOH groups in single APOSS, different arrangements of multiple APOSSes can also affect the packing parameter.109 A well-controlled model is PS-APOSS hybrids with different numbers/topologies of APOSS cages. As shown in Figure 11b, hybrid molecules with the same linear topology but different numbers of APOSS cages on main chain, and hybrid molecules with the same number of APOSS cages, one is linear while another is branched. As observed from dynamic light scattering (DLS) and TEM techniques, the PS-A1 (PS chain with one APOSS cage) can self-assemble into vesicles due to its small volume fraction and cross-section area of APOSS, which favors the large packing parameter for vesicular structures. By increasing the number of APOSS cages to three and five with the same linear topology (PS-A3 and PS-A5, respectively),


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the large cross-section areas of 3APOSSes and 5APOSSes decrease the packing parameter and worm-like micelles are formed. Meanwhile, hybrids with different topologies also show distinct solution behaviors. The branched PS-A5 are found to self-assemble into condensed, spherical micelles – different from the worm-like micelles formed by linear PS-A5. As the APOSSes are charged, both electrostatic repulsion and steric hindrance will force them to further stay away from each other in the branched case, which accordingly results into significant increase of cross-section area as well as the decrease of packing parameter to favor the spherical micelles.

Figure 11. (a) Chemical structure of PS-APOSS and different self-assembled morphologies in various solvents with final water content of 50 wt %. From left to right: 1,4-dioxane, DMF, and DMF/NaOH, respectively. Reprinted with permission from ref 108. Copyright 2010 American Chemical Society. (b) Changes of molecular topology and number of APOSS cages determine the packing parameter (p) and consequently lead to the morphological transitions in a PS-APOSS system. Adapted with permission from ref 109. Copyright 2016 Royal Society of Chemistry.


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ENHANCING THE HYBRID PROPERTIES VIA SELF-ASSEMBLY The self-assembly processes provide a strategy to organize hybrid molecules into well-ordered supramolecular structures. Compared to single molecular state, these well-ordered structures can exhibit enhanced properties (e.g., catalytic and fluorescent) by forming local concentrated environments. One example is emulsion catalysis for biphasic reactions. Wei’ group grafted alkyl tails onto the catalytic hexavanadate clusters to make a series of hybrids (Figure 12a),110 which self-assemble into vesicles in aqueous solution containing H2O2 as oxidant. When another reactant thiophen (in hexane) is added to the aqueous solution with stirring, stable emulsions are formed with most catalytic hexavanadates located at the water-hexane interface (Figure 12c), where two reactants can meet and react. For typical catalytic reactions involving two or more immiscible reactants (H2O2 and thiophen here), the rate is low because the reactions can only occur at the limited interfacial area. Therefore, the emulsions formed by amphiphilic hybrids provides an approach to dramatically increase the interfacial area, and to place the catalysts at the same locations as well, which significantly enhances the catalytic efficiency. The emulsions can also be applied to make latex nanoparticles. We grafted Keggin-type clusters by four organic tails with methyl methacrylate (MMA) end groups, and the hybrid molecules can form stable emulsions in water/styrene mixed solutions (Figure 12d).111 As both organic tails and styrene have active double bonds, the emulsions can undergo polymerization to create core-shell latex nanoparticles. The nanoparticles fully covered by catalytically active Keggins have average hydrodynamic radius (Rh) of ~80 nm, which can be easily recycled by centrifugation. Moreover, the core-shell structure also shows high stability in various organic solvents due to the crosslinking between Keggins and PS cores, further extending its applications as quasi-homogeneous catalysts.


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Figure 12. (a) Molecular structure of hexavanadate-based hybrids. (b) Schematic illustration of biphasic catalytic reactions. (c) Picture of typical emulsion solution containing hexavanadatebased hybrids, the deeper color in the middle indicates that most of hybrids are located at interfacial area between two immiscible solvents. Reprinted with permission from ref 110. Copyright 2012 Wiley-VCH. (d) Schematic illustration of the core-shell latex nanoparticles formed by emulsion polymerization. Reprinted with permission from ref 111. Copyright 2015 Royal Society of Chemistry. Besides the spherical morphology, the self-assembly approach can also lead to the formation of nanobelts (similar to the bilayer phase in surfactant systems) with high surface area. The amphiphilic hybrids composed of hexavanadate clusters and long alkyl tails (Figure 13a) are found to form one-dimensional aggregates with micrometer scale in length, but only nanometer scale in thickness.112 High-resolution TEM images reveal that the polar hexavanadate clusters are packed on the surface of the nanobelts (Figure 13b). Such nanobelts fully covered with


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catalytically active hexavanadate clusters are promising high-efficiency heterogeneous catalysts. Indeed, the nanobelts can significantly improve the efficiency of catalyzed oxidative desulfurization with hydrogen peroxide. Meanwhile, the nanobelts also show high stability and can be easily re-collected after reaction.

Figure 13. (a) Chemical structure of hybrid molecules and illustration of catalytic reaction on the surface of the self-assembled nanobelts. (b) High-resolution TEM image showing the detailed packing of hexavanadate clusters on the nanobelts. Adapted with permission from ref 112. Copyright 2014 Wiley-VCH. Supramolecular structures with fluorescence properties responsive to external stimuli is also attractive. For this purpose, two pyrene groups are symmetrically attached to the Lindqvist-type clusters by Hill’s group (Figure 14a).90 The hybrids can form vesicles in polar solvents due to their amphiphilic properties. When the original counterions (TBA+) are replaced by H+, the solution shows interesting pH-dependent fluorescence response. The fluorescence signals are (Figure 14b) due to the π-π interaction between the pyrene groups, and controlled by the spatial distance between two pyrenes.113 When the vesicles are formed, the pyrene groups can be close to each other in the hydrophobic domain. On the other hand, pyrene-pyrene distance is largely affected by the curvature of vesicles, which is in turn controlled by the attractive forces between the hybrids. Accordingly, the self-assembly strategy here demonstrates a simple way to control the


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fluorescence properties of the hybrids and can be used as an indicator to detect the solution environment via the change of the intermolecular interaction among the hybrids. The correlations among the fluorescence signals, vesicle size, and the Zeta potential of vesicles are consistent (Figure 12c-e), which highlights the potential applications of this strategy.

Figure 14. (a) Molecular structure of Lindqvist-pyrene hybrids and schematic illustration of the vesicle formation. (b) Fluorescence spectra of vesicle solutions at different pH. (c) Change of pyrene excimer/monomer intensity ratio, (d) vesicle size, and (e) Zeta potential of vesicles at different solution pH. Reprinted with permission from ref 90. Copyright 2011 American Chemical Society. CONCLUSIONS AND OUTLOOK New synthetic approaches to chemically link organic functional groups onto the macroionic clusters with precise control lead to various well-defined inorganic-organic molecular hybrids. They demonstrate complicated solution behaviors due to the presence of several different


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intermolecular attractive forces during their microphase (self-assembly) and macrophase separation processes. In solution, the behaviors of such hybrid molecules are mainly regulated by the competition between the counterion-mediated attraction and other types of attractive forces such as hydrogen bonding, hydrophobic interaction and cation-π interaction, which consequently determines whether their self-assembly behaviors follow the rules of macroions or amphiphilic surfactants. The incorporation of organic groups can significantly increase flexibility of the hybrids, and as a result can lead to some interesting stimuli-responsive properties. Through the manipulation of molecular architectures and external conditions, various self-assembled morphologies can be achieved. We also demonstrate that the self-assembly approach can provide a feasible way to enhance the properties of hybrids. Based on the current achievements in macroionic cluster-based hybrid systems, several directions may deserve more attentions in future. (1) The inorganic-organic hybrids attached by chiral ligands are possible to show chiral selection to modulate the interactions between hybrids and other chiral molecules. (2) By incorporating the organic molecules with different shapes/symmetries especially rigid components such as rod, disc, and polyhedron, the corresponding hybrids may exhibit more versatile self-assembled structures. (3) In current hybrid systems, the macroionic clusters only contain one type of charge (positive or negative), it should be interesting to explore the hybrids consist of both positively and negatively charged clusters and to compare their solution behaviors with common zwitterionic surfactants or polyelectrolytes. (4) Incorporating different type of macroioinc clusters with various sequences/architectures will also be attractive. For example, by connecting different clusters on main chain like peptides, or different clusters onto tetrahedrons/dendrimers. (5) Taking advantages of porous features on blackberry


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surface and their delicately adjustable intermolecular distance, it would be interesting to develop approaches to accurately adjust this distance to achieve some tunable physical properties.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. Notes The authors declare no competing financial interest. ACKNOWLEDGEMENTS T.L. acknowledges support by NSF (CHE-1607138) and the University of Akron.

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Table of Contents

The Competition and Cooperation among Different Attractive Forces in the Solutions of Inorganic-Organic Hybrids Containing Macroionic Clusters

The macroionic cluster-based hybrids present as a good model to study the competition and cooperation among different attractive forces.

Jiancheng Luo and Tianbo Liu*


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Biographies

Tianbo Liu received his B.S. degree in Chemistry from Peking University in 1994. In 1999, he received his Ph.D. in Chemistry from the SUNY at Stony Brook, where he studied block copolymer solutions by using scattering techniques with Professor Benjamin Chu. After spending two more years in the same group as a Postdoctoral Associate, he started his independent research career at Physics Department, Brookhaven National Laboratory in 2001. He joined Department of Chemistry, Lehigh University in 2005 as an Assistant Professor, and was promoted to the Associate Professor in 2009 and then Full Professor in 2012. He moved to the Department of Polymer Science, The University of Akron as A. Schulman Professor in 2013 and now is serving as the Department Chair. His laboratory focuses on understanding the fundamental physical chemistry of complex fluids, especially the intermolecular interaction, self-assembly and phase behaviors of hydrophilic macroions, inorganic-organic hybrids and other colloidal and biological solution systems.


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Langmuir

Jiancheng Luo received his B.S. degree in Polymer Material Science and Engineering from the East China University of Science and Technology (ECUST) in 2014. He received his M.S. degree in Polymer Science from the University of Akron in 2015, under the supervision of Professor Tianbo Liu. After that, he started his Ph.D. degree in the same research group and now is a Ph.D. candidate in Department of Polymer Science, the University of Akron. His research mainly focuses on the synthesis and self-assembly of inorganic-organic hybrids based on polyoxometalate and fullerene (C60) clusters. He is also interested in exploring the macroion-counterion interaction and chiral selection in solution.


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