Aggregation and Tunable Color Emission Behaviors of l-Glutamine-Derived Platinum(II) Bipyridine Complexes by Hydrogen-Bonding, π-π Stacking and Metal-Metal Interactions.

An l-glutamine-derived functional group was introduced to the bis(arylalkynyl)platinum(II) bipyridine complexes 1-4. The emission could be switched between the 3 MLCT excited state and the triplet excimeric state through solvent or temperature changes, which is attributed to the formation and disruption of hydrogen-bonding, π-π stacking, and metal-metal interactions. Different architectures with various morphologies, such as honeycomb nanostructures and nanospheres, were formed upon solvent variations, and these changes were accompanied by 1 H NMR and distinct emission changes. Additionally, yellow and red emissive metallogels were formed at room temperature due to the different aggregation behaviors introduced by the substituent groups on bipyridine. The thermoresponsive metallogel showed emission behavior with tunable colors by controlling the temperature. The negative Gibbs free-energy change (ΔG) and the large association constant for excimer formation have suggested that the molecules undergo aggregation through hydrogen-bonding, π-π, and metal-metal interactions, resulting in triplet excimeric emission.

A rational molecular design of triazine-containing alkynylplatinum(ii) terpyridine complexes and the formation of helical ribbons via PtPt, π-π stacking and hydrophobic-hydrophobic interactions.

The self-assembly of triazine-containing alkynylplatinum(ii) terpyridine complexes has revealed the formation of sophisticated helical ribbons. Fine control of the morphological transition from plates to helical structures has been demonstrated through an interplay of the bent molecular structure and PtPt, π-π stacking and hydrophobic-hydrophobic interactions.

Self-Assembled Architectures of Alkynylplatinum(II) Amphiphiles and Their Structural Optimization: A Balance of the Interplay Among Pt···Pt, π-π Stacking, and Hydrophobic-Hydrophobic Interactions.

A series of alkynylplatinum(II) terpyridine complexes with triethylene glycol units was synthesized, and their self-assembly properties were investigated in solution by UV-vis absorption, emission, and 1H NMR spectroscopy. The aggregation behaviors of several water-soluble complexes were investigated in aqueous media. Some of them were found to give rise to uniform fibers, suggesting the important role that triethylene glycol units has in regulating their self-assembly properties. Further modifications of these structures through the incorporation of alkyl chains and changes in counter-anions have rendered the complexes more amphiphilic in nature, and the effect of their alkyl chain lengths was studied and optimized. The distinguishable color and spectral changes upon variations in solvent compositions might have potential applications in developing colorimetric and luminescent probes for the detection of microenvironment change. Furthermore, an optimum chain length, i.e., n-butyl chain, is required for the formation of stable and ordered nanostructures. This represents a delicate balance among Pt···Pt, π-π stacking, and hydrophobic-hydrophobic interactions and provides guiding principles into the construction of supramolecular materials with practical applications.

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.