Circularly polarized luminescence of pinene-modified tetradentate platinum(II) enantiomers containing fused 5/6/6 metallocycles.

In this study, a couple of tetradentate Pt(II) enantiomers ((-)-1 and (+)-1) and a couple of tetradentate Pt(IV) enantiomers ((-)-2 and (+)-2) containing fused 5/6/6 metallocycles have been synthesized by controlling reaction conditions. Two valence forms could transform into each other through mild chemical oxidants and reductants. Single-crystal X-ray diffraction confirms the structures of (-)-1 and (-)-2. The coordination sphere of the Pt(II) cation in (-)-1 displays a distorted square-planar geometry and a platinum centroid helix chirality. In contrast, the structure of (-)-2 reveals a distorted octahedral geometry. The solution and the solid of (-)-1 are highly luminescent. Complex (-)-1 shows a prominent aggregation-induced emission enhancement (AIEE) behavior in DMSO/water solution with emission quantum yield (Φ em) up to 73.2%. Furthermore, highly phosphorescent Pt(II) enantiomers exhibit significant circularly polarized luminescence (CPL) with a dissymmetry factor (g lum) of order 10-3 in CH2Cl2 solutions at room temperature. Symmetrically appreciable CPL signals are observed for the enantiomers (-)-1 and (+)-1.

Mechanochromic luminescence properties of fluoro-substituted pinene-containing cyclometalated platinum(II) complexes with multiple triplet excited states.

The structure-mechanochromism relationship is explored with respect to packing patterns and corresponding intermolecular interactions that are affected by the number and location of -F. The distinct and reversible mechanochormic luminescence (Δλem up to ca. 90 nm) of yellow solids (-)-1-Yg, (-)-2-Yg, and (-)-3-Yg was displayed with a simultaneous crystal-to-amorphous transformation. The change of multiple triplet excited states accounted for the mechanochormic luminescence, and a switch from the 3π,π* monomer to the excimer/3MMLCT occurred in the grinding process. The mechanical force led to perturbation in the molecular packing, and aggregates with effective PtPt and π-π interactions were formed in the amorphous phase, leading to the variation of excited states. The mechanochromic luminescence could be reverted by dropping in CH2Cl2 and could be cycled multiple times without perceivable performance degradation. This work gives a reference for designing mechanochromic luminescent materials toward multicolor and multicomponent responses.

Enhanced Circularly Polarized Luminescence Activity in Chiral Platinum(II) Complexes With Bis- or Triphenylphosphine Ligands.

Distinct circularly polarized luminescence (CPL) activity was observed in chiral (C∧N∧N)Pt(II) [(C∧N∧N) = 4,5-pinene-6'-phenyl-2,2'-bipyridine] complexes with bis- or triphenylphosphine ligands. Compared to the pseudo-square-planar geometry of chiral (C∧N∧N)Pt(II) complexes with chloride, phenylacetylene (PPV) and 2,6-dimethylphenyl isocyanide (Dmpi) ligands, the coordination configuration around the Pt(II) nucleus of chiral (C∧N∧N)Pt(II) complexes with bulk phosphine ligands is far more distorted. The geometry is straightforwardly confirmed by X-ray crystallography. The phosphines' participation enhanced the CPL signal of Pt(II) complexes profoundly, with the dissymmetry factor (g lum) up to 10-3. The distorted structures and enhanced chiroptical signals were further confirmed by time-dependent density functional theory (TD-DFT) calculations.

Highly efficient removal of Cu(ii) by novel dendritic polyamine-pyridine-grafted chitosan beads from complicated salty and acidic wastewaters.

In this study, dendritic polyamine chitosan beads with and without 2-aminomethyl pyridine were facilely prepared and characterized. Compared to CN (without the pyridine function), more adsorption active sites, larger pores, higher nitrogen content, higher specific surface area, and higher strength could be obtained for CNP (with the pyridine function). CNP microspheres afforded a larger adsorption capacity than those obtained by CN for different pH values; further, the uptake amounts of Cu(ii) were 0.84 and 1.12 mmol g-1 for CN and CNP beads, respectively, at pH 5. The CNP microspheres could scavenge Cu(ii) from highly acidic and salty solutions: the maximum simulated uptake amount of 1.93 mmol g-1 at pH 5 could be achieved. Due to the strong bonding ability and weakly basic property of pyridine groups, the adsorption capacity of Cu(ii) at pH 1 was 0.75 mmol g-1 in highly salty solutions, which was comparative to those obtained from the commercial pyridine chelating resin M4195 (Q Cu(II) = 0.78 mmol g-1 at pH 1). In addition, a distinct salt-promotion effect could be observed for CNP beads at both pH 5 and 1. Therefore, the prepared adsorbent CNP beads can have promising potential applications in the selective capturing of heavy metals in complex solutions with higher concentrations of H+ and inorganic salts, such as wastewaters from electroplating liquid and battery industries.

PtPt interaction triggered tuning of circularly polarized luminescence activity in chiral dinuclear platinum(ii) complexes.

Circularly polarized luminescence (CPL) activity switched by PtPt interaction is disclosed in two couples of dinuclear Pt(ii) complex enantiomers. Upon varying the length of the bridging ligand, intramolecular metal-metal interaction manipulation is achieved as evidenced from crystal structures. Complex (-)-1 exhibiting strong PtPt interaction displays red phosphorescence with a maximum peak at 638 nm, while complex (-)-2 exhibiting weak PtPt interaction displays green phosphorescence with a maximum peak at 530 nm. The observed CPL was opposite in sign for the two complexes. TD-DFT simulations further confirmed the influence of the PtPt distance on the difference in the electronic optical activities.

Solvent-tuned charge-transfer properties of chiral Pt(ii) complex and TCNQ˙- anion adducts.

A new pair of adducts comprising one chiral Pt(ii) complex cation, [Pt((-)-L1)(Dmpi)]+ ((-)-1) or [Pt((+)-L1)(Dmpi)]+ ((+)-1) [(-)-L1 = (-)-4,5-pinene-6'-phenyl-2,2'-bipyridine, (+)-L1 = (+)-4,5-pinene-6'-phenyl-2,2'-bipyridine, Dmpi = 2,6-dimethylphenylisocyanide], together with one TCNQ˙- anion have been obtained, and the structures have been confirmed via single-crystal X-ray crystallography and infrared (IR) spectroscopy. The chiral Pt(ii) cation and TCNQ˙- anion are dissociated in MeOH solution, while charge transfer adducts are formed in H2O solution, leading to perturbation of the electronic structure and alteration of the chiral environment, as evidenced by the differences in the UV-vis absorption and electronic circular dichroism spectra. The solvent-tuned charge-transfer properties also have been validated through emission and resonance light scattering spectra. The interesting findings may have potential applications in the development of black absorbers and wide band gap semiconductors.