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. Mechanism studies clearly reveal that this asymmetric electron migration environment and hybrid n-π* and π-π* instincts are responsible for the afterglow and radical radiance at ambient conditions. Moreover, we demonstrate the applications of colorful CPPL for displays and encryption via manipulation of both excitation and observation times.

Stimuli-responsive luminescence from polar cyano/isocyano-derived luminophores via 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, etc., 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. Among them, donor-acceptor (D-A) derived unimolecular and co-assembled luminophores have attracted more attention because their large delocalized structures and noncovalent interaction recognition sites can rebuild the electronic transfer character in the aggregative state, thus endowing them with outstanding stimuli-responsive luminescent behavior via intermolecular and intramolecular charge transfer in polytropic morphologies. In this perspective paper, we give a brief introduction on stimuli-responsive organic and coordinated luminophores and the documented typical design concepts and applications in recent years. It is expected that this perspective article will not only summarize the recent developments of polar cyano/isocyano-derived luminophores and their coordination compounds via structural tailoring and self-assembly but also throw light on the future of the design of more sophisticated stimuli-responsive architectures and their versatile properties.

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. Experiments and theoretical calculations revealed the existence of the unusual radical mechanism and electron-deficient character of novel phosphahelicenes. These rigid quaternary bonding skeletons facilitated versatile fluorescence with good tunability and excellent efficiency. Moreover, the enantiomerically enriched crystals of phosphahelicenes emitted intense circularly polarized luminescence (CPL). Notably, the modulated CPL of racemic phosphahelicenes was induced by chiral transmission in the cholesteric mesophase, showing ultrahigh asymmetry factors of CPL (+0.51, -0.48). Our findings provide a new approach for the design of emissive phosphahelicenes towards chiral emitters and synthesized precursors.

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 Mn2+-Cu2+ 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 Mn2+-Cu2+ 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 Co2+ ion for forming double-[1 + 1] and [2 + 2] metallacycles involving the H2pdd precursor and the [1 + 1] Cu2+ complex for double-[1 + 1] and [2 + 2] macrocycles containing the H2hpdd unit, respectively. The structural diversity is originated from the non-perfect match between [1 + 1]/[2 + 2] Schiff-base macrocycles and dinuclear metal centers; hence, a compromise between the metal coordination modes and alterations of the ligand conformation takes place.

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

A series of trinuclear lanthanide circular helicates [Ln3L3]Cl3 have been synthesized via supramolecular subcomponent self-assembly. Photophysical studies demonstrate that the unique helical bis-tetradentate 1,29-dialdehyde ligand L2- could serve as an effective sensitizer for SmIII, EuIII, NdIII and YbIII 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 (PDPA) 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 (S,S-1a, R,R-1b) could be obtained, having S,S/R,R-1,2-diaminocyclohexane (S,S/R,R-DACH) precursors, while Cu(II) ion template only resulted in a mononuclear Schiff-base Cu(II) acyclic complex (S,S-2) accompanied by the half-oxidation of PDPA 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 S,S-2 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. In fact, corresponding [2 + 2] dinuclear Cu(II) macrocycles and even metal-free macrocycles unsuitable for direct synthesis can be obtained via Cd(II) → Cu(II) transmetalation and Na2S demetalation verified by ESI-MS and UV-vis spectra. In addition, control experiments indicate that the synthesis of metal-free macrocycles via the direct nontemplate method merely results in the mixture of multiple components of [1 + 1], [2 + 2], and [3 + 3] Schiff-base macrocycles, and they are difficult to isolate.

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 CO2 adsorption over CH4 is demonstrated by the gas adsorption experiment.

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

A new flexible 2-ethylthiophene pendant-armed dialdehyde (H2tdd) 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 ZnII complex 1, 18-membered [1 + 1] mononuclear ZnII macrocycles 2-4, chiral/racemic 34-membered [2 + 2] dinuclear ZnII complexes 5-9, and 46-membered [2 + 2] dinuclear ZnII macrocycles 10-12 via ZnII 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] ZnII 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. Interestingly, a solvent-induced single-crystal-to-single-crystal transformation was first achieved for two types of solvated mononuclear macrocycles 3a and 3b (H2O vs CH3CN) with folded and unfolded ligand conformations. In addition, the photoluminescent properties were studied for this family of Schiff-base macrocyclic ZnII complexes as well as the dialdehyde precursor H2tdd.

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 P1, P2 and P3 were successfully synthesized via the Pd-catalyzed Stille cross-coupling copolymerization approach, with 6,8-Dibromo-3,3-bis-decyl-3,4-dihydro-2H-thieno[3,4-b][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)-2H-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 P1, P2, and P3, 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. Also, three copolymers showed good performance in electrochromic parameters, which mainly consists of optical contrast, response time, and coloration efficiency. In general, the excellent electrochromic performances of the copolymers make them outstanding candidates for electrochromic material applications.