Self-assembly of a nonanuclear NiII cluster via atmospheric CO2 fixation: synthesis, structure, collision-induced dissociation mass spectrometry and magnetic property†
Abstract
A novel nonanuclear nickel(II) cluster identified as [Ni9(OH)6(CO3)2(ba)8(Hdmpz)6(DMF)2]·EtOH·2DMF (SD/Ni9a, Hba = benzoic acid, Hdmpz = 3,5-dimethyl-1H-pyrazole) is successfully constructed from mixed ligands. The single-crystal X-ray diffraction (SCXRD) structural analysis confirms the composition and reveals the “drum-like” inner core structure surrounded by ba− and DMF. Six Hdmpz ligands in their neutral form further sandwich the “drum” up and down, and is hydrogen bonded with two carbonate anions that are derived from the atmospheric CO2 with the help of Et3N. Electrospray ionization mass spectrometry (ESI-MS) reveals that the SD/Ni9a maintains an intact core in the solution with a slight exchange of outer ligands. Detailed collision-induced dissociation (CID) experiments reveal the collision energy (CE)-promoted ligand loss and exchange between ba− and Hdmpz. Furthermore, the magnetic study shows that there is no interaction between the Ni centers at room temperature, whereas the ferromagnetic coupling between the Ni centers is found with an S = 3 spin ground state of the cluster at low temperature. Moreover, the UV-vis spectrum and the photocurrent response measurements show its good optical properties with an indirect bandgap of about 2.35 eV and fast current response upon visible light irradiation.
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