Effects of length alteration of OPE-containing mono- and dinuclear alkynylplatinum(II) terpyridine complexes on photophysical, structural and morphological properties

A series of mononuclear complexes and unsymmetric dinuclear alkynylplatinum(II)terpyridine complexes with oligo(paraphenylene ethynylene)(OPE)-derived backbone with a variation of the lengths of alkoxy chains and OPE backbones was synthesized.The morphological properties,packing lattice and gelation behaviors of the mononuclear complexes were systematically studied,and the thermodynamic parameters and packing lattices of the dinuclear complexes were also investigated,providing further insights into the roles of the non-covalent interactions and their delicate balance in constructing sophisticated supramolecular architectures.Metallogel and nanotube formation have been observed upon a delicate control of the intermolecular interactions by altering the lengths and structural dimensions of the complexes.

Novel conductive metallo-supramolecular polymer AIE gel for multi-channel highly sensitive detection of hydrazine hydrate

Hydrazine hydrate(DH)is an important fine chemical intermediate and as fuel for rockets,however,it also has serious toxic for humans and environment.Developing novel materials and methods for sensitive detection of DH in water and air is an important task.In order to effectively detect DH,a novel conductive supramolecular polymer metallogel(PQ-Ag)has been constructed by the coordination of bis-5-hydroxyquinoline functionalized pillar[5]arene(PQ5)with Ag+.The metallogel PQ-Ag could realize the multi-channel sensitive detection of DH through naked-eye,fluorescence,and electrochemical methods.The lowest limit of detection(LOD)is 0.1 mg/m^(3)in air and 2.68×10^(−8)mol/L in water,which is lower than the standard of the US Environmental Protection Agency(EPA)for DH of maximum allowable concentration in drinking water.More importantly,an electronic device for DH detection based on the metallogel PQ-Ag was designed and prepared,which can realize conveniently and efficiently multi-channel detection and alert of DH through sound and light alarms not only in water but also in air.

Hierarchical self-assembly of crown ether based metal-carbene cages into multiple stimuli-responsive cross-linked supramolecular metallogel

The hierarchical self-assembly(HSA) strategy widely utilized in biological systems has been applied in artificial systems to orchestrate small building blocks into complex functional architectures. The non-interfering interactions glue various building blocks together and produce new species with attractive properties. Herein, we functionalized NHC-based assemblies with orthogonal host–guest interaction to fabricate metal-carbene based supramolecular polymer gel. A series of unique crown etherappended cylinder-like trinuclear AuIhexacarbene assemblies [Au_(3)(L)_(2)](PF_(6))_(3)(L=D1–D4, A1–A4) were synthesized from the corresponding trisimidazolium salts H_(3)-L(PF_(6))_(3)(L=D1–D4, A1–A4) in which the N-wingtip of the imidazole moieties were substituted with three identical crown ether groups of different sizes(B15C5, B18C6, B21C7, DB24C8). The gold carbene assembly is able to complex six ammonium salts without disrupting the underlying metal-carbene cylinders. In addition, the supramolecular polymer metallogel featuring a multiple-responsiveness can be formed by using [Au_(3)(A_(4))_(2)](PF_(6))_(3) appended with DB24C8 as the core and bisammonium salt as the cross-linker. The case of introducing orthogonal interaction to NHC moiety by N-wingtip substitution demonstrates the feasibility and the power of such strategy to expand the NHC-based supramolecular system and endow them with novel properties.

CONTROLLED FABRICATION OF ONE-DIMENSIONAL POLYMER NANOSTRUCTURES via METALLOGEL TEMPLATE POLYMERIZATION

A facile method is reported to controllably fabricate one dimensional （1D） polymer nan,astructures via metallogel template polymerization. The metallogel was prepared through coordination interactions between silver ions and a ligand （L） bearing three pyridyl groups in tetrahydrofuran （THF）. The diameters of the metallogel nanofibers could be tuned by the gel concentration （GC）. Due to its high thermal stability and facility of removal, the metallogel was used as the template for radical polymerization of diacryolyl-2,6-diaminopyridine （DADAP） to form poly-diacryolyl-2,6-diaminopyridine （PDADAP） nanostructures. The gradually eroding of the templates by PDADAP provided us an effective way to fabricate various nanostructures of the polymer. We have demonstrated that different 1D nanostructures, including n^noribbons, nanotubes and nanowires, could be selectively fabricated by adjusting polymerization time, monomer concentration and GC. The rheological properties of the gel samples were tested by a rheometer. As prolonging the reaction time, more and more polymers were formed and the strength of the resulting polymer gels became higher and higher. The simple preparation process, easy controlled microstructures and adequate gel strength would make it a facile synthetic method for different 1D polymer nanosturctures.