Geometrical manipulation of complex supramolecular tessellations by hierarchical assembly of amphiphilic platinum(II) complexes.

Here we report complex supramolecular tessellations achieved by the directed self-assembly of amphiphilic platinum(II) complexes. Despite the twofold symmetry, these geometrically simple molecules exhibit complicated structural hierarchy in a columnar manner. A possible key to such an order increase is the topological transition into circular trimers, which are noncovalently interlocked by metal···metal and π-π interactions, thereby allowing for cofacial stacking in a prismatic assembly. Another key to success is to use the immiscibility of the tailored hydrophobic and hydrophilic sidechains. Their phase separation leads to the formation of columnar crystalline nanostructures homogeneously oriented on the substrate, featuring an unusual geometry analogous to a rhombitrihexagonal Archimedean tiling. Furthermore, symmetry lowering of regular motifs by design results in an orthorhombic lattice obtained by the coassembly of two different platinum(II) amphiphiles. These findings illustrate the potentials of supramolecular engineering in creating complex self-assembled architectures of soft materials.

Living supramolecular polymerization achieved by collaborative assembly of platinum(II) complexes and block copolymers.

An important feature of biological systems to achieve complexity and precision is the involvement of multiple components where each component plays its own role and collaborates with other components. Mimicking this, we report living supramolecular polymerization achieved by collaborative assembly of two structurally dissimilar components, that is, platinum(II) complexes and poly(ethylene glycol)-b-poly(acrylic acid) (PEG-b-PAA). The PAA blocks neutralize the charges of the platinum(II) complexes, with the noncovalent metal-metal and π-π interactions directing the longitudinal growth of the platinum(II) complexes into 1D crystalline nanostructures, and the PEG blocks inhibiting the transverse growth of the platinum(II) complexes and providing the whole system with excellent solubility. The ends of the 1D crystalline nanostructures have been found to be active during the assembly and remain active after the assembly. One-dimensional segmented nanostructures with heterojunctions have been produced by sequential growth of two types of platinum(II) complexes. The PAA blocks act as adapters at the heterojunctions for lattice matching between chemically and crystallographically different platinum(II) complexes, achieving heterojunctions with a lattice mismatch as large as 21%.

Rational Design of Multi-Stimuli-Responsive Scaffolds: Synthesis of Luminescent Oligo(ethynylpyridine)-Containing Alkynylplatinum(II) Polypyridine Foldamers Stabilized by Pt···Pt Interactions.

A series of oligo(ethynylpyridine)-containing alkynylplatinum(II) terpyridine/bzimpy (bzimpy = 2,6-bis(N-alkylbenzimidazol-2'-yl)pyridine) metallofoldamers has been designed and synthesized to investigate the potential applications of metallofoldamers imparted by the rich spectroscopic responses of Pt···Pt interactions. Apart from the control of the folding/unfolding processes by solvent compositions and temperatures, this class of metallofoldamers has also been found to exhibit reversible folding/unfolding behaviors mediated by the addition of acids/bases due to the incorporation of the acid-sensitive oligo(ethynylpyridine) derivatives. More importantly, the intramolecular Pt···Pt interaction has been found to play a crucial role in governing the folded state conformation. The conformation of this class of metallofoldamers has been investigated by 2D ROESY NMR, electronic absorption, and emission spectroscopy, which provide further insights into the rational molecular design and multidimensional control of metallofoldamers upon the application of various external stimuli, leading to the preparation of multi-stimuli-responsive materials for potential applications in material sciences.

Multiresponsive Luminescent Cationic Cyclometalated Gold(III) Amphiphiles and Their Supramolecular Assembly.

A new class of amphiphilic tridentate cyclometalated gold(III) complexes has been designed and synthesized as luminescent supramolecular building blocks. Positively charged trimethylammonium (-CH2NMe3+) containing alkynyl ligands have been incorporated to introduce the electrostatic interactions. The X-ray crystal structures of two of the complexes have been determined, and the existence of π-π interactions between molecules has been observed. Steady-state and time-resolved absorption and emission studies have been carried out to investigate the nature of the excited states. The complexes are found to exhibit self-assembly properties with the assistance of π-π stacking and hydrophobic interactions and possibly weak Au···Au interaction, resulting in notable emergence of low-energy absorption bands and luminescence changes. The presence of a large hydrophobic moiety is found to be crucial for the formation of aggregates, especially in polar media where hydrophobic interactions play an important role. The nature of the counterion has been shown to have a significant effect on the extent of self-assembly in different media. Upon aggregation, nanofibers are formed in polar media, while nanorods are observed in nonpolar media in one of the representative complexes. Interestingly, a small modification on the alkynyl ligand resulted in the formation of nanoribbons instead. Intriguing luminescence mechanochromic properties have also been observed. This orthogonal and rational molecular design strategy has been shown to be effective in the construction of gold(III)-based smart and multiresponsive materials.

Self-assembly of alkynylplatinum(II) terpyridine amphiphiles into nanostructures via steric control and metal-metal interactions.

A series of mono- and dinuclear alkynylplatinum(II) terpyridine complexes containing the hydrophilic oligo(para-phenylene ethynylene) with two 3,6,9-trioxadec-1-yloxy chains was designed and synthesized. The mononuclear alkynylplatinum(II) terpyridine complex was found to display a very strong tendency toward the formation of supramolecular structures. Interestingly, additional end-capping with another platinum(II) terpyridine moiety of various steric bulk at the terminal alkyne would lead to the formation of nanotubes or helical ribbons. These desirable nanostructures were found to be governed by the steric bulk on the platinum(II) terpyridine moieties, which modulates the directional metal-metal interactions and controls the formation of nanotubes or helical ribbons. Detailed analysis of temperature-dependent UV-visible absorption spectra of the nanostructured tubular aggregates also provided insights into the assembly mechanism and showed the role of metal-metal interactions in the cooperative supramolecular polymerization of the amphiphilic platinum(II) complexes.

Energy Landscape in Supramolecular Coassembly of Platinum(II) Complexes and Polymers: Morphological Diversity, Transformation, and Dilution Stability of Nanostructures.

Establishment of energy landscape has emerged as an efficient pathway for improved understanding and manipulation of both thermodynamic and kinetic behaviors of complicated supramolecular systems. Herein, we report the establishment of energy landscapes of supramolecular coassembly of platinum(II) complexes and polymers, as well as the fabrication of nanostructures with enhanced complexity and intriguing properties from the coassembly systems. In the energy landscape, coassembly at room temperature has been found to only allow the longitudinal growth of platinum(II) complexes and block copolymers into core-shell nanofibers that are the kinetically trapped products. Thermal annealing can switch on the transverse growth of platinum(II) complexes and block copolymers to produce core-shell nanobelts that are the thermodynamically stable nanostructures. The extents of the transverse growth are found to increase with thermal annealing temperatures, leading to nanobelts with larger widths. Besides, rapid quenching of a hot coassembly mixture to room temperature can capture intermediate nanobelt- block-nanofiber nanostructures that are metastable and capable of converting to nanobelts upon further incubation at room temperature. Moreover, sonication treatment has been found to couple with the energy landscape of the coassembly system and open a unique energy-driven pathway to activate the kinetically forbidden nanofiber-to-nanobelt morphological transformation. Furthermore, based on the established energy landscapes, nanosphere- block-nanobelt nanostructures with distinct segmented architectures have been fabricated by thermal annealing of the ternary mixture of platinum(II) complexes, block copolymers, and polymer brushes in a one-pot and single-step procedure. Finally, the nanobelts and nanosphere- block-nanobelt nanostructures are found to possess intriguing morphological stability against acid and dilution, exhibiting characteristics that are important for promising biomedical applications.

Controlling Self-Assembly Mechanisms through Rational Molecular Design in Oligo( p-phenyleneethynylene)-Containing Alkynylplatinum(II) 2,6-Bis( N-alkylbenzimidazol-2'-yl)pyridine Amphiphiles.

The systematic control over association mechanisms of self-assembled materials has been demonstrated through the rational design and synthesis of a series of amphiphilic dinuclear alkynylplatinum(II) bzimpy (bzimpy = 2,6-bis( N-alkylbenzimidazol-2'-yl)pyridine) complexes containing the shape-persistent oligo( p-phenyleneethynylene)s. Multistage morphological transformations from plates to fibers and to spherical nanostructures under different solvent compositions have been demonstrated. The subtle balances between multiple noncovalent interactions including Pt···Pt, hydrophobic, hydrophilic, and π-π stacking interactions are found to have profound impact on the supramolecular assembly of the system, in which a change in the association mechanism from isodesmic to cooperative and back to isodesmic growth has been observed upon increasing hydrophilicity of the complexes.

Formation of 1D Infinite Chains Directed by Metal-Metal and/or π-π Stacking Interactions of Water-Soluble Platinum(II) 2,6-Bis(benzimidazol-2'-yl)pyridine Double Complex Salts.

A new class of water-soluble double complex salts (DCSs), [Pt{bzimpy(TEG)2}Cl][Pt{bzimpy(PrSO3)2}Cl] and its alkylplatinum(II) bzimpy derivatives (bzimpy = 2,6-bis(benzimidazol-2'-yl)pyridine, has been demonstrated to exhibit strong aggregation in water through Pt···Pt and π-π stacking interactions to give a variety of distinctive nanostructures based on the formation of one-dimensional (1D) infinite chains. The self-association process can be systemically controlled by varying the solvent composition and temperature and has been studied by 1H NMR, 2D NOESY NMR, mass spectrometry, electron and confocal fluorescence microscopy, UV-vis absorption, and emission spectroscopy.

Directional Self-Assembly and Photoinduced Polymerization of Diacetylene-Containing Platinum(II) Terpyridine Complexes.

A series of newly designed and synthesized diacetylene-containing platinum(II) terpyridine complexes exhibited intriguing self-assembly properties. Facilitated by Pt⋅⋅⋅Pt, π-π stacking, hydrogen-bonding and hydrophobic-hydrophobic interactions, these complexes are preorganized to readily undergo topochemical polymerization reactions upon photoirradiation. The in situ polymerization of the diacetylene units to form polydiacetylene, indicated by the UV/Vis spectral changes, gel permeation chromatography and dynamic light scattering, was found to alter their assembly behaviours, as revealed by TEM images.

Synthesis of Luminescent Platinum(II) 2,6-Bis(N-dodecylbenzimidazol-2'-yl)pyridine Foldamers and Their Supramolecular Assembly and Metallogel Formation.

Dinuclear alkynylplatinum(II) metallofoldamers with an oligomeric m-phenyleneethynylene backbone have been designed with the incorporation of a sterically undemanding, π-conjugated, and hydrophobic 2,6-bis(N-dodecylbenzimidazol-2'-yl)pyridine pincer ligand. The complex with the optimal chain length has been found to exhibit gelation behavior via stabilization by noncovalent Pt···Pt and π-π stacking interactions in the hierarchical architecture constructed from the single-turn helix. The chain lengths of the complexes have been found to be a critical determinant for their gelation behavior, conformations, and morphologies. Such a gelation process has been found to undergo a cooperative assembly mechanism according to the nucleation-elongation model. Their self-assembly via the Pt···Pt and π-π stacking interactions has been studied by 1H NMR, 2D ROESY NMR (ROESY = rotating-frame Overhauser spectroscopy), electronic absorption, and emission spectroscopy, and density functional theory calculations have provided further insights into the folded state geometry of this class of metallofoldamers.

Metal-Metal and π-π Interactions Directed End-to-End Assembly of Gold Nanorods.

The end-to-end aggregation of gold nanorods (GNRs) has been demonstrated to be directed by a thioacetate-containing alkynylplatinum(II) terpyridine complex. The in situ deprotected complex is preferentially attached at the ends of the gold nanorods (GNRs) and induce the aggregation of GNRs in an "end-to-end" manner by Pt···Pt and π-π interactions, which have been characterized by electron microscopy, energy dispersed X-ray (EDX) analysis, and UV-vis absorption spectroscopy. The assembly of the nanorods into chain-like nanostructures can be controlled by the concentration of the Pt(II) complexes.

Tuning of Supramolecular Architectures of l-Valine-Containing Dicyanoplatinum(II) 2,2'-Bipyridine Complexes by Metal-Metal, π-π Stacking, and Hydrogen-Bonding Interactions.

A series of newly synthesized dicyanoplatinum(II) 2,2'-bipyridine complexes exhibits self-assembly properties in solution after the incorporation of the l-valine amino units appended with various hydrophobic motifs. These l-valine-derived substituents were found to have critical control over the aggregation behaviors of the complexes in the solution state. On one hand, one of the complexes was found to exhibit interesting circularly polarized luminescence (CPL) signals at low temperature due to the formation of chiral spherical aggregates in the temperature-dependent studies. On the other hand, systematic transformation from less uniform aggregates to well-defined fibrous and rod-like structures via Pt⋅⋅⋅Pt and π-π stacking interactions has also been observed in the mixed-solvent studies. These changes were monitored by UV/Vis absorption, emission, circular dichroism (CD), and CPL spectroscopies, and morphologies were studied by electron microscopy.

Synthesis, Electrochemistry, and Photophysical Studies of Ruthenium(II) Polypyridine Complexes with D-π-A-π-D Type Ligands and Their Application Studies as Organic Memories.

A new class of ruthenium(II) polypyridine complexes with a series of D-π-A-π-D type (D=donor, A=acceptor) ligands was synthesized and characterized by 1 H NMR spectroscopy, mass spectrometry, and elemental analysis. The photophysical and electrochemical properties of the complexes were also investigated. The newly synthesized ruthenium(II) polypyridine complexes were found to exhibit two intense absorption bands at both high-energy (λ=333-369 nm) and low-energy (λ=520-535 nm) regions. They are assigned as intraligand (IL) π→π* transitions of the bipyridine (bpy) and π-conjugated bpy ligands, and IL charge-transfer (CT) transitions from the donor to the acceptor moiety with mixing of dπ(RuII )→π*(bpy) and dπ(RuII )→π*(L) MLCT characters, respectively. In addition, all complexes were demonstrated to exhibit intense red emissions at approximately λ=727-744 nm in degassed dichloromethane at 298 K or in n-butyronitrile glass at 77 K. Nanosecond transient absorption (TA) spectroscopy has also been carried out, establishing the presence of the charge-separated state. In order to understand the electrochemical properties of the complexes, cyclic voltammetry has also been performed. Two quasi-reversible oxidation couples and three quasi-reversible reduction couples were observed. One of the ruthenium(II) complexes has been utilized in the fabrication of memory devices, in which an ON/OFF current ratio of over 104 was obtained.

Dynamic scaffold of chiral binaphthol derivatives with the alkynylplatinum(II) terpyridine moiety.

Platinum(II)-containing complexes with inherently chiral binaphthol derivatives display a versatile scaffold between random coils and single-turn helical strands, in which the conformational transition is controlled by the Pt···Pt and π-π interactions of alkynylplatinum(II) terpyridine moiety upon solvent and temperature modulation. The bisignate Cotton effect in the circular dichroism spectra is indicative of the cooperative transformation from random coil state to a compact single-turn M- or P-helix. More importantly, as revealed by the appearance of new UV-vis absorption and emission bands during conformational change, the self-assembly of the platinum(II)-containing complex into a helical structure is assisted by the metal···metal and π-π interactions of the alkynylplatinum(II) terpyridine moieties. The folded structure with stabilization via metal···metal and π-π interactions has been supported by density functional theory calculations, which provide insights into the folded geometry of these kind of metallo-foldamers.

Transformable nanostructures of platinum-containing organosilane hybrids: non-covalent self-assembly of polyhedral oligomeric silsesquioxanes assisted by Pt···Pt and π-π stacking interactions of alkynylplatinum(II) terpyridine moieties.

An alkynylplatinum(II) terpyridine complex functionalized with polyhedral oligomeric silsesquioxanes (POSS) moieties has been demonstrated to exhibit self-association behavior to give various distinguishable nanostructures with interesting morphological transformation from rings to rods in response to solvent conditions through the stabilization of Pt···Pt and π-π stacking interactions as well as hydrophobic-hydrophobic interactions. These changes can be systemically controlled by varying the solvent composition and have been studied by (1)H NMR, electron microscopy, UV-vis absorption, and emission spectroscopies.

Luminescent cyclometalated alkynylplatinum(II) complexes with a tridentate pyridine-based N-heterocyclic carbene ligand: synthesis, characterization, electrochemistry, photophysics, and computational studies.

A new class of luminescent alkynylplatinum(II) complexes with a tridentate pyridine-based N-heterocyclic carbene (2,6-bis(1-butylimidazol-2-ylidenyl)pyridine) ligand, [Pt(II)(C^N^C)(C≡CR)][PF6], and their chloroplatinum(II) precursor complex, [Pt(II)(C^N^C)Cl][PF6], have been synthesized and characterized. One of the alkynylplatinum(II) complexes has also been structurally characterized by X-ray crystallography. The electrochemistry, electronic absorption and luminescence properties of the complexes have been studied. Nanosecond transient absorption (TA) spectroscopy has also been performed to probe the nature of the excited state. The origin of the absorption and emission properties has been supported by computational studies.

Single-turn helix-coil strands stabilized by metal···metal and π-π interactions of the alkynylplatinum(II) terpyridyl moieties in meta-phenylene ethynylene foldamers.

Dinuclear alkynylplatinum(II) terpyridyl complexes with oligomeric bridge consisting of five repeating meta-phenylene ethynylene (mPE) units have been found to exhibit a strong tendency to fold back onto themselves to form short helical strands through the stabilization of Pt···Pt and π-π interactions. The steric bulk of the terpyridine ligands and the length of the oligomeric bridge have been found to affect the extent of the intramolecular Pt···Pt interaction that governs the stabilization of the short helical strand in solution. Their folding properties via Pt···Pt and π-π stacking interactions have been studied by (1)H NMR, 2D ROESY NMR, electronic absorption, and emission spectroscopies.

Platinum(II) Probes for Sensing Polyelectrolyte Lengths and Architectures.

Platinum(II) polypyridine complexes of a square-planar geometry have been used as spectroscopic reporters for quantification of various charged species through non-covalent metal-metal interactions. The characterization of molecular weights and architectures of polyelectrolytes represents a challenging task in polymer science. Here, we report the utilization of platinum(II) complex probes and non-covalent metal-metal interactions for sensing polyelectrolyte lengths and architectures. It is found that the platinum(II) probes can bind to linear polyelectrolytes via electrostatic attractions and give rise to significant spectroscopic changes associated with the formation of metal-metal interactions, and the extent of the spectroscopic changes is found to increase with the lengths of the linear polyelectrolytes. Besides, the platinum(II) probes have been found to co-assemble with the linear polyelectrolytes to form well-defined nanofibers, and the lengths of the linear polyelectrolytes can be directly estimated from the diameter of the nanofibers under transmission electron microscopy observation. Interestingly, upon mixing with the platinum(II) probes, polyelectrolytes with bottlebrush architectures have been found to exhibit larger spectroscopic changes than linear polyelectrolytes with the same chemical composition. Combined with the reported theoretical studies on counterion condensation of polyelectrolytes, the platinum(II) complexes are found to function as spectroscopic probes for sensing the charge densities of the polyelectrolytes with different lengths and diverse architectures. Moreover, platinum(II) probes pre-organized in nanostructured aggregates have been found to intercalate into double-stranded DNA, which are naturally occurring biological polyelectrolytes with helical architectures and intercalation sites, to give significant enhancement of spectroscopic changes when compared to the intercalation of monomeric platinum(II) probes into double-stranded DNA.