Promising CO2 Capture and Effective Iodine Adsorption of Hyper-Cross-Linked Conjugated Porous Organic Polymers Prepared from a Cyclopentannulation Reaction.

Three novel conjugated porous organic polymers, denoted as C-POP1-3 and which consist of alternating pyrene cores with various contorted fluorene surrogates, were successfully synthesized from a versatile one-pot palladium-catalyzed [3+2] cyclocondensation reaction. The resulting polymers were obtained in excellent yields and displayed weight-average molecular weights (Mw) ranging from 12.2 to 20.2 kg/mol with polydispersity indices (Mw/Mn) ranging between 1.8 and 2.4, suggesting that the molecular masses are narrowly distributed and thus implying homogeneous polymer chains. Thermal stability exploration of C-POP1-3 by thermogravimetric analysis (TGA) revealed an impressive robustness with a 10% weight reduction temperature attaining 485 °C. Investigation of the inherent microporosity properties of C-POP1-3 via nitrogen adsorption experiments using Brunauer-Emmett-Teller (BET) theory discloses their surface areas which reach up to 560 m2 g-1 and pore volumes averaging 0.47 cm3 g-1. The target conjugated polymers were explored as adsorbents disclosing a maximum carbon dioxide adsorption of 83.0 mg g-1 at 273 K and low pressure for C-POP1, whereas iodine sorption tests portrayed prominent outcomes, notably for C-POP3 which proved to owe a strong affinity toward the hitherto mentioned halogen by achieving a maximum adsorption of 2220 mg g-1. Additionally, recyclability experiments confirmed the possibility to regenerate the polymers' adsorption capabilities even after seven consecutive cycles of adsorption-desorption cycles, which qualify them as auspicious iodine adsorbents.

Recent Advances in the Catalytic Synthesis of the Cyclopentene Core.

Five-membered carbocycles are ubiquitously found in natural products, pharmaceuticals, and other classes of organic compounds. Within this category, cyclopentenes deserve special attention due to their prevalence as targets and as well as key intermediates for synthesizing more complex molecules. Herein, we offer an overview summarizing some significant recent advances in the catalytic assembly of this structural motif. A great variety of synthetic methodologies and strategies are covered, including transition metal-catalyzed or organocatalyzed processes. Both inter- and intramolecular transformations are documented. On this ground, our expertise in the application of C-H functionalization reactions oriented towards the formation of this ring and its subsequent selective functionalization is embedded.

High Uptake of the Carcinogenic Pararosaniline Hydrochloride Dye from Water Using Carbazole-Containing Conjugated Copolymers Synthesized from a One-Pot Cyclopentannulation Reaction.

Three conjugated copolymers CAP1-3 were synthesized in one-step via a typical [3+2] cyclopentannulation reaction using a specially designed diethynyl carbazole synthon with various dibrominated polycondensed aromatic hydrocarbons (PAHs). The desired copolymers CAP1-3 were obtained in excellent yields, and their structures were confirmed by 1H- and 13C- nuclear magnetic spectroscopy (NMR), whereas gel permeation chromatography revealed weight-average molar masses (Mw) up to 19.9 kDa with a polydispersity index (PDI) in the range of 2.2-2.6. Interestingly, CAP1-3 exhibits an outstanding capacity to adsorb the carcinogenic pararosaniline hydrochloride dye (Basic Red 9, BR9) from aqueous solutions. Isothermal adsorption studies were carried out following the linear models of Langmuir and Freundlich, divulging an adsorption capacity maximum (qm) toward BR9 of 483.09 mg g-1. Investigation of the dye uptake mechanism on CAP1-3 revealed a pseudo-second-order kinetic model for the target copolymer that showed the highest uptake capacity. Recyclability tests disclosed an excellent adsorption efficiency of BR 9 reaching 93% after six cycles.

Azaarenes: 13 Rings in a Row by Cyclopentannulation.

Cyclopentannulation was explored as a strategy to access large, stable azaarenes. Buchwald-Hartwig coupling of previously reported di- and tetrabrominated cyclopentannulated N,N'-dihydrotetraazapentacenes furnished stable azaarenes with up to 13 six-membered rings in a row and a length of 3.1 nm. Their optoelectronic and semi-conducting properties as well as their aromaticity were investigated.

Tetra(peri-naphthylene)anthracene: A Near-IR Fluorophore with Four-Stage Amphoteric Redox Properties.

A novel, benign synthetic strategy towards soluble tetra(peri-naphthylene)anthracene (TPNA) decorated with triisopropylsilylethynyl substituents has been established. The compound is perfectly stable under ambient conditions in air and features intense and strongly bathochromically shifted UV/vis absorption and emission bands reaching to near-IR region beyond 900 nm. Cyclic voltammetry measurements revealed four facilitated reversible redox events comprising two oxidations and two reductions. These remarkable experimental findings were corroborated by theoretical studies to identify the TPNA platform a particularly useful candidate for the development of functional near-IR fluorophores upon appropriate functionalization.

A Symmetrically π-Expanded Carbazole Incorporating Fluoranthene Moieties.

A novel doubly cyclopentannulated carbazole which is accessible through a successive π-expansion of di(1-naphthylamine) is disclosed. The carbazole moiety is generated in the final step through intramolecular oxidative coupling. The π-expansion of carbazole resulted in strongly altered optoelectronic and electrochemical properties. The solid-state structure features an interesting packing motif with alternating face-to-face π⋅⋅⋅π and edge-to-face C-H⋅⋅⋅π interactions. The experimental findings were corroborated by theoretical calculations.

Cyclopentannulated Dihydrotetraazapentacenes.

The transition-metal-catalyzed cyclization of bissilylethynylated N,N'-dihydrotetraazapentacene (TIPS-TAP-H2 ) into bissilylated cyclopenta[fg,qr]pentacenes is reported. Depending on the catalyst either none, one or two silyl groups migrate and change their positions in the formed five-membered rings. The optoelectronic properties are quite similar, whereas the packing motifs differ dramatically. Control experiments and quantum chemical calculations were performed to investigate the mechanism of the reaction and the selectivity of the silyl shift.

Cyclopenta[b]annulation of Heteroarenes by Organocatalytic γ'[C(sp3 )-H] Functionalization of Ynones.

A new approach for the cyclopenta[b]annulation of heteroarenes through metal-free and directing-group-free γ'[C(sp3 )-H] functionalization and intramolecular hydroalkylation of ynones has been developed. In an unprecedented event, nucleophilic addition of an organophosphine to the designed ynones triggers γ'[C(sp3 )-H] functionalization, leading to the formation of heteroaryl-based ortho-quinodimethane (oQDM) intermediates that undergo carbocyclization to provide cyclopentannulated heteroarenes in good yields and excellent stereoselectivities. Deuterium-labeling experiments substantiated the proposed reaction mechanism as well as the speculated epimerization.