Double-Model Decay Strategy Integrating Persistent Photogenic Radicaloids with Dynamic Circularly Polarized Doublet Radiance and Triplet Afterglow.

Organic phosphors integrating circularly polarized persistent luminescence (CPPL) across the visible range are widespread for applications in optical information encryption, bioimaging, and 3D display, but the pursuit of color-tunable CPPL in single-component organics remains a formidable task. Herein, via in situ photoimplanting radical ion pairing into axial chiral crystals, we present and elucidate an unprecedented double-module decay strategy to achieve a colorful CPPL through a combination of stable triplet emission from neutral diphosphine and doublet radiance from photogenic radicals in an exclusive crystalline framework. Owing to the photoactivation-dependent doublet radiance component and an inherent triplet phosphorescence in the asymmetric environment, the CPL vision can be regulated by altering the photoactivation and observation time window, allowing colorful glow tuning from blue and orange to delayed green emission.

Stimuli-responsive luminescence from polar cyano/isocyano-derived luminophores structural tailoring and self-assembly.

Polar cyano fragments and their isomeric isocyano counterparts have attracted great attention as stimuli-responsive luminescent materials in a wide range of fields including organic light-emitting diode devices, chemical fluorescent sensors, photoelectric semiconductors, anti-counterfeit products, ., mainly because of their typical electron-deficient activity, noncovalent recognition ability, and variable coordination capacity. The electron-deficient and polar nature of these blocks have significant effects on the properties of the cyano/isocyano-based luminophore materials, especially concerning their condensed state-dependent electronic structures.

Mn(iii)-mediated C-P bond activation of diphosphines: toward a highly emissive phosphahelicene cation scaffold and modulated circularly polarized luminescence.

Transition metal mediated C-X (X = H, halogen) bond activation provides an impressive protocol for building polyaromatic hydrocarbons (PAHs) in C-C bond coupling and annulation; however, mimicking both the reaction model and Lewis acid mediator simultaneously in a hetero-PAH system for selective C-P bond cleavage faces unsolved challenges. At present, developing the C-P bond activation protocol of the phosphonic backbone using noble-metal complexes is a predominant passway for the construction of phosphine catalysts and P-center redox-dependent photoelectric semiconductors, but non-noble metal triggered methods are still elusive. Herein, we report Mn(iii)-mediated C-P bond activation and intramolecular cyclization of diphosphines by a redox-directed radical phosphonium process, generating phosphahelicene cations or phosphoniums with nice regioselectivity and substrate universality under mild conditions.

Tunable Construction of Sandwich-Type Double-[1 + 1] and Half-Folded [2 + 2] Schiff-Base Complexes Controlled by the Combination of Primary and Secondary Template Effects.

The first-row transition-metal ions Mn-Cu could serve as effective templates to construct three types of double-[1 + 1], [2 + 2], and [1 + 1] Schiff-base dinuclear macrocyclic complexes in the presence of dialdehydes with different pendant arms and a common 1,8-diamine. The extremely flexible nature of macrocyclic ligands allows for the multiple template-directed syntheses, but the final products could be finely tuned by the subtle variations of Mn-Cu ions in a 3d-electronic configuration, radius, and coordination number/geometry as well as the auxiliary (pendant-armed and anionic) template effect at the same time. Two borderlines are observed at the Co ion for forming double-[1 + 1] and [2 + 2] metallacycles involving the Hpdd precursor and the [1 + 1] Cu complex for double-[1 + 1] and [2 + 2] macrocycles containing the Hhpdd unit, respectively.

Self-assembly and luminescence of trinuclear lanthanide based supramolecular circular helicates.

A series of trinuclear lanthanide circular helicates [LnL]Cl have been synthesized supramolecular subcomponent self-assembly. Photophysical studies demonstrate that the unique helical bis-tetradentate 1,29-dialdehyde ligand L could serve as an effective sensitizer for Sm, Eu, Nd and Yb ions exhibiting efficient characteristic fluorescence emission because of the shell-type blocking of the ligand, which makes them the first circular helicates exhibiting near-infrared lanthanide fluorescence.

Transmetalation and Demetallization for Open-Oyster-like Non-Ionic Cd(II) Macrocycles.

This work designed a nonionic extended dialdehyde 6,6'-(phenylazanediyl)dipicolinaldehyde () for constructing Schiff-base macrocyclic complexes with weaker metal-ligand interactions, so as to solve the long-standing challenges of transmetalation and demetallization in macrocyclic complexes. An enantiomeric pair of open-oyster-like 26-membered [2 + 2] Schiff-base macrocyclic dinuclear Cd(II) complexes (,-, ,-) could be obtained, having ,/,-1,2-diaminocyclohexane (,/,-) precursors, while Cu(II) ion template only resulted in a mononuclear Schiff-base Cu(II) acyclic complex (,-) accompanied by the half-oxidation of instead of expected [2 + 2] Cu(II) macrocyclic complexes. It is suggested that the weak oxidization capability of Cu(II) ion is responsible for the formation of ,- because X-ray photoelectron spectroscopy (XPS) for the solid powder of reaction mixture of direct Cu(II) ion template synthesis implies that both Cu(I) and Cu(II) species are present.

Solvent-controlled self-assembly of tetrapodal [4 + 4] phosphate organic molecular cage.

Two flexible subcomponents, namely tris(4-formylphenyl)phosphate and tris(2-aminoethyl)amine, are assembled into a tetrapodal [4 + 4] cage depending on the solvent effect. Single-crystal structure analysis reveals that the caivity is surrounded by four phosphate uints. Good selectivity of CO adsorption over CH is demonstrated by the gas adsorption experiment.

Construction and Photoluminescent Properties of Schiff-Base Macrocyclic Mono-/Di-/Trinuclear Zn Complexes with the Common 2-Ethylthiophene Pendant Arm.

A new flexible 2-ethylthiophene pendant-armed dialdehyde (Htdd) was reacted with 1,3-propanediamine, [( S, S),( R, R),(±)]-1,2-diaminocyclohexane, and 1,2-bis(2-aminoethoxy)ethane, giving birth to 36-membered [2 + 2] Schiff-base macrocyclic trinuclear Zn complex 1, 18-membered [1 + 1] mononuclear Zn macrocycles 2-4, chiral/racemic 34-membered [2 + 2] dinuclear Zn complexes 5-9, and 46-membered [2 + 2] dinuclear Zn macrocycles 10-12 via Zn ion template-assisted Schiff-base condensation. It is worth mentioning that the secondary template effects for nitrate and halide counterions have been observed in the 1,3-propanediamine involved imine condensation. In all [2 + 2] Zn macrocycles, dinuclear complexes 5-9 display a full-folded molecular conformation, while trinuclear complex 1 and dinuclear complexes 10-12 exhibit distinct half-folded structures in the presence or absence of intramolecular π-π stacking interactions between two phenolic rings of the dialdehyde component.

Donor-Acceptor-Type Copolymers Based on 3,4-Propylenedioxy-thiophene and 5,6-Difluorobenzotriazole: Synthesis and Electrochromic Properties.

Three solution-processable D-A-type conjugated polymers , and were successfully synthesized via the Pd-catalyzed Stille cross-coupling copolymerization approach, with 6,8-Dibromo-3,3-bis-decyl-3,4-dihydro-2-thieno[3,4-][1,4] dioxepine (M1) and 2,5-Bis(trimethylstannanyl)thiophene (M3) as the donor units and 4,7-Dibromo-5,6-difluoro-2-(2-hexyl-decyl)-2-benzotriazole (M2) as the acceptor unit, wherein the feed ratio of the three units was 1:3:4 (M1:M2:M3, the same below), 1:1:2 and 3:1:4 for , , and , respectively. The results obtained by our test showed that the feed ratio between the D and A units had a significant effect on both the electrochemical and the spectroelectrochemical properties of the three polymers. The copolymers exhibited a gradually deepening red color in neutral state with the increase of M1 content and then turned to a transmissive grey color in the oxidation state.