Self-assembly of conformation-adaptive dihydrophenazine-based coordination cages.

In this study, we designed and synthesized three conformation-adaptive Pd2L4- and Pd3L6-type coordination cages based on three dihydrophenazine-based ligands with different lengths. Interestingly, the shorter ligands L1 and L2 self-assembled into Pd2L4-type coordination cages while the longer ligand L3 formed Pd3L6-type one, mainly driven by the anion template effect. All coordination cages were confirmed through single-crystal X-ray diffraction, and their structural conformations underwent great changes compared with those of their corresponding ligands. Moreover, the conformational changes also significantly affected their photophysical and electrochemical properties which were distinct from their parent ligands.

Functionalization of Pentacene: A Facile and Versatile Approach to Contorted Polycyclic Aromatic Hydrocarbons.

In this work, a facile and versatile strategy for the synthesis of contorted polycyclic aromatic hydrocarbons (PAHs) starting from the functionalized pentacene was established. A series of novel PAHs 1-4 and their derivatives were synthesized through a simple two-step synthesis procedure involving an intramolecular reductive Friedel-Crafts cyclization of four newly synthesized pentacene aldehydes 5-8 as a key step. All the molecules were confirmed by single-crystal X-ray diffraction and their photophysical and electrochemical properties were studied in detail. Interestingly, the most striking feature of 1-4 is their highly contorted carbon structures and the accompanying helical chirality. In particular, the optical resolution of 2 was successfully achieved by chiral-phase HPLC, and the enantiomers were characterized by circular dichroism and circularly polarized luminescence spectroscopy. Despite the highly nonplanar conformations, these contorted PAHs exhibited emissive properties with moderate-to-good fluorescence quantum yields, implying the potential utility of this series PAHs as high-quality organic laser dyes. By using a self-assembly method with the help of epoxy resin, a bottle microlaser based on 3 a was successfully illustrated with a lasing wavelength of 567.8 nm at a threshold of 0.3 mJ/cm2 . We believe that this work will shed light on the chemical versatility of pentacene and its derivatives in the construction of novel functionalized PAHs.

Octalithium, Tetrasodium, and Decalithium Compounds Based on Pyrrolyl Ligands: Synthesis, Structures, and Activation of the C-H Bonds of Pyrrolyl Rings and C═N Bonds of a Series of Ligands by Organolithium Reagents.

The organometallic compounds of lithium ions have garnered continuous interest as indispensable precursors for the syntheses of organometallic complexes of main-group metals, transition metals, lanthanide metals, and actinide metals. In this work, we present a strategy for the preparation of a series of polynuclear lithium complexes. This methodology features the utilization of organolithium reagents both as metal sources to coordinate with the ligands and as nucleophilic reagents to undergo nucleophilic addition to the C═N bonds of the ligands. Reaction of a ligand HL1 [HL1 = 2-(((1-(2-(dimethylamino)ethyl)-1H-pyrrol-2-yl)methylene)amino)phenol] with n-BuLi produced complex [Li8(L1a)4]·1.5Tol (1·1.5Tol) [H2L1a = 2-((1-(1-(2-(dimethylamino)ethyl)-1H-pyrrol-2-yl)pentyl)amino)phenol]. One prominent feature regarding the formation of 1·1.5Tol is the occurrence of nucleophilic addition of n-BuLi to the C═N bond of HL1, leading to the generation of a new [L1a]2- ligand that contains both aminophenol and 1-(2-pyrrolyl)alkylamine scaffolds. The developed protocol can be adapted to a series of organolithium reagents. Compounds [Li8(L1b)4] (2) and [Li8(L1c)4] (3) were afforded by treatment of HL1 with sec-BuLi and LiCH2SiMe3, respectively. Reaction of an analogous ligand HL2 [HL2 = 2-(((1-(2-(dimethylamino)ethyl)-1H-pyrrol-2-yl)methylene)amino)-4-methylphenol] with n-BuLi generated compound [Li8(L2a)4] (4). C═N bond activation was not observed in the reaction of HL1 with NaOtBu, and the complex [Na4(L1)4]·Tol (5·Tol) was obtained. A decanuclear complex [Li10(L3a)2(L3b)2] (6) was also prepared via the reaction of HL3 [HL3 = 2-(2-((((1H-pyrrol-2-yl)methylene)amino)methyl)-1H-pyrrol-1-yl)-N,N-dimethylethan-1-amine] with t-BuLi. A remarkable feature in terms of the synthesis of 6 is the simultaneous occurrence of hydrogen atom abstraction from the C-H bond of the pyrrolyl ring and nucleophilic addition to the C═N bond of the HL3 ligand by t-BuLi. A series of amines containing biologically and physiologically important moieties were achieved by hydrolysis of the crude products from the reactions of the HL1-HL3 ligands and organolithium reagents. This work provides an efficient approach to high-nuclearity lithium compounds as well as a series of amines.

Extended phenothiazines: synthesis, photophysical and redox properties, and efficient photocatalytic oxidative coupling of amines.

Herein we successfully developed a ring-fusion approach to extend the conjugation length of phenothiazines and synthesized a series of novel extended phenothiazines 1-5. The intriguing π-conjugation length-dependent photophysical and redox properties of 1-5, and their photocatalytic performance towards visible-light-driven oxidative coupling reactions of amines were systematically investigated. The results indicated that this series of extended phenothiazines exhibited continuous red shifts of light absorption with increasing numbers of fused rings. As compared with the conventional phenothiazine (PTZ), all the extended phenothiazines displayed reversible redox behavior and maintained a strong excited-state reduction potential as well. Consequently, 3, 4 and 5 with longer effective conjugation lengths could efficiently catalyze the oxidative coupling of amines to imines under visible-light irradiation; by comparison, the shorter 1, 2 and PTZ could only catalyze such reactions in the presence of UV light. Moreover, 3 showed superior catalytic performance which can result in better yields within a shorter reaction time, and in a broad substrate scope. Finally, a direct and efficient conversion of amines to imines under sunlight in an air atmosphere was successfully realized. We believe that our study including the new phenothiazine modification methodology and the newly developed extended phenothiazine-based photocatalysts will open up a new way to develop novel phenothiazine-based materials for optoelectronic and catalytic applications.

Post-Synthetic Modification of Metal-Organic Frameworks Bearing Phenazine Radical Cations for aza-Diels-Alder Reactions.

Metal-organic frameworks (MOFs) consisting of organic radicals are of great interest because they have exhibited unique and intriguing optical, electronic, magnetic, and chemo-catalytic properties, and thus have demonstrated great potential applications in optical, electronic, and magnetic devices, and as catalysts. However, the preparation of MOFs bearing stable organic radicals is very challenging because most organic radicals are highly reactive and difficult to incorporate into the framework of MOFs. Herein we reported a post-synthetic modification strategy to prepare a novel MOF containing phenazine radical cations, which was used as heterogeneous catalyst for aza-Diels-Alder reaction. The zinc-based metal-organic framework Zn2 (PHZ)2 (dabco) (N) was successfully synthesized from 5,10-di(4-benzoic acid)-5,10-dihydrophenazine (PHZ), triethylene diamine (dabco) with Zn(NO3 )2 ⋅ 6H2 O by solvothermal method. The as-synthesized MOF N was partially oxidized by AgSbF6 to form MOF R containing ∼10% phenazine radical cation species. The resultant MOF R was found to keep the original crystal type of N and very persistent under ambient conditions. Consequently, MOF R was successfully employed in radical cation-catalyzed aza-Diels-Alder reactions with various imine substrates at room temperature with high reaction conversion. Moreover, heterogeneous catalyst MOF R was reusable up to five times without much loss of catalytic activity, demonstrating its excellent stability and recyclability. Therefore, the post-synthetic modification developed in this work is expected to become a versatile strategy to prepare radical-based MOFs for the application of heterogeneous catalysts in organic synthesis.

The fluorescent probe based on methyltetrahydroxanthylium skeleton for the detection of hydrazine.

Two probes based on tetrahydroxanthylium unit (probe 1a) and methyltetrahydroxanthylium unit (probe 1b) were designed and synthesized for the detection of hydrazine. Probes 1a-b exhibited turn-on red emission signal and high selectivity toward NH2NH2. The response time of probe 1a to NH2NH2 was more than 60 min, while that of probe 1b was less than 30 min. The detection limits of probes 1a-b were calculated as 210 nM and 110 nM respectively. What's more, the tolerance experiments showed that methyltetrahydroxanthylium unit possessed higher tolerance toward nucleophiles. Moreover, cells imaging experiments demonstrated that probe 1b could detect exogenous NH2NH2 in living HeLa cells.

Fluorescent hydrogen sulfide probes based on azonia-cyanine dyes and their imaging applications in organelles.

Three hydrogen sulfide (H2S) probes based on an azonia-cyanine skeleton were successfully designed and prepared. Probe 1a, containing 4-chloro-7-nitro-1,2,3-benzoxadiazole connected to the cyanine dye, had an emission at 660 nm that was enhanced 4.5-fold by the reduced photoinduced electron transfer process when reacting with H2S. Probes 1b and 1c were constructed from cyanine dyes with electron withdrawing 2,4-dinitrophenyl and 7-nitrobenzo[c] [1,2,5]oxadiazol-4-yl groups, respectively. Probes 1b and 1c gave off-on type responses with 169- and 17-fold fluorescent enhancements at 639 nm with H2S. Their emission properties were influenced by intramolecular hydrogen bonds and intramolecular charge transfer processes. The detection limits of probes 1a-1c were calculated at 178, 121, and 9.6 nM, respectively. The intracellular imaging experiments with HeLa cells indicated probe 1a was a mitochondria-targeting H2S probe, while probes 1b and 1c were lysosome-targeting H2S probes.