3837-38-5Relevant articles and documents
Functionalization of Zirconium-Based Metal–Organic Layers with Tailored Pore Environments for Heterogeneous Catalysis
Dang, Dongbin,Lollar, Christina T.,Pang, Jiandong,Qiao, Guan-Yu,Qin, Jun-Sheng,Rao, Heng,Yu, Jihong,Yuan, Shuai,Zhou, Hong-Cai
, p. 18224 - 18228 (2020)
Intriguing properties and functions are expected to implant into metal–organic layers (MOLs) to achieve tailored pore environments and multiple functionalities owing to the synergies among multiple components. Herein, we demonstrate a facile one-pot synthetic strategy to incorporate multiple functionalities into stable zirconium MOLs via secondary ligand pillaring. Through the combination of Zr6-BTB (BTB=benzene-1,3,5-tribenzoate) layers and diverse secondary ligands (including ditopic and tetratopic linkers), 31 MOFs with multi-functionalities were systematically prepared. Notably, a metal–phthalocyanine fragment was successfully incorporated into this Zr-MOL system, giving rise to an ideal platform for the selective oxidation of anthracene. The organic functionalization of two-dimensional MOLs can generate tunable porous structures and environments, which may facilitate the excellent catalytic performance of as-synthesized materials.
Efficient Synthesis of Anthraquinones from Diaryl Carboxylic Acids via Palladium(II)-Catalyzed and Visible Light-Mediated Transformations
Kim, Kiho,Min, Minsik,Hong, Sungwoo
supporting information, p. 848 - 852 (2017/03/11)
Irradiation of 9-ester-substituted anthracenes with visible light results in the formation of endoperoxides in the absence of a photocatalyst, which further undergo base-assisted fragmentation to afford anthraquinones. The excited state species of anthracene generated by energy transfer, interacts with 3O2 to afford 1O2 by energy transfer and undergoes cycloaddition with 1O2. By employing palladium(II)-catalyzed and visible light-mediated transformations, we have developed an efficient synthetic protocol for accessing diverse anthraquinones from readily available diaryl carboxylic acids. The optimal result was obtained with palladium(II) acetate, Ac-Ile-OH, benzoquinone and potassium carbonate in tert-amyl alcohol under O2 at 90 °C with irradiation from a 30 W fluorescent light bulb. (Figure presented.).
Rigid Core Anthracene and Anthraquinone Linked Nitronyl and Iminoyl Nitroxide Biradicals
Akpinar, Handan,Schlueter, John A.,All?o Cassaro, Rafael A.,Friedman, Jonathan R.,Lahti, Paul M.
, p. 4051 - 4059 (2016/07/19)
The first syntheses of bis(nitronyl nitroxide) and bis(iminoyl nitroxide) (diNN, diIN) biradicals linked through rigid acene core conjugating anthracene (A) and anthraquinone (AQ) units are reported. Computational modeling predicts weak intramolecular exchange in AQ-linked systems, but A-linked biradicals to have ground state multiplicities consistent with the Borden-Davidson disjointness model. Solution electron spin resonance spectra showed inter-radical exchange-coupled triplet states, except for 2,6-AQ biradicals showing isolated spin spectra. Crystallography of the A-linked biradicals shows a key role for inter-radical contacts for molecular packing. DiINs showed lower-dimensional dyad packing with disorder at the radical units: the conformationally more symmetrical diNNs gave staircase one-dimensional or brickwork two-dimensional lattices. Core anthracene unit stacking was only seen in two systems with bromine on the central anthracene ring: the (large) bromine occupies alternate side placement in dyad stacks for the diIN, chain stacks for the diNN. Magnetism of 2,7-A-linked systems showed predominant ferromagnetic intramolecular triplet-singlet splitting of 24-28 K for diNNs and 8 K for diINs, plus weak antiferromagnetic (AFM) interactions from intermolecular contacts. The 2,6-A-linked biradicals showed AFM exchange between spins. Both A and AQ cores offer possibilities for electronic material development, with a combination of multiple radical spins and π-electron-rich acene cores.
