A 2-D organic–inorganic supramolecular layer based on a {P₂Mo₅} cluster bridged by Mn(II) and pentanuclear fragment linker

Abstract

An organic–inorganic hybrid based on {P₂Mo₅} clusters, (H₂bim)₃[{Na_0.5(H₂O)_0.5}₂{Mn(OH)₄(H₂O)₂}{Na_0.5(H₂bim)}₂{Mn(H₂O)₄(P₂Mo₅O₂₃)₂}]·4H₂O (1) (bim = 2,2′-biimidazole), was hydrothermally synthesized and characterized by elemental analyses, IR, TG, UV, and single crystal X-ray diffraction analyses. In 1, four Na ions, one Mn, and two bim ligands are linked by four μ–O bridges to form unusual pentanuclear fragments [{Na_0.5(H₂O)_0.5}₂{Mn(OH)₄(H₂O)₂}{Na_0.5(H₂bim)}₂]. Each pentanuclear segment links adjacent to four Standberg units to form supramolecular dimer chains, which are further connected by Mn(H₂O)₄ linkers to yield infinite 2-D layer. Two kinds of cage-like pores are observed in alternating type along the crystallographic b axis in which protonated H₂bim ligands fill one sort of pores. Electrochemical and fluorescent properties of 1 have been investigated.

Graphical Abstract

Mn²⁺ and unusual pentanuclear fragments {[Na_0.5(H₂O)_0.5]₂Mn(OH)₄(H₂O)₂[Na_0.5(H₂bim)]₂} are introduced into {P₂Mo₅} system to yield an infinite 2-D supramolecular layer with two cage-like pores. Compound 1 displays good electrocatalytic activity on reduction of hydrogen peroxide, and fluorescent properties in the solid state at room temperature.

Keywords:

• Hydrothermal synthesis
• [P₂Mo₅O₂₃]⁶⁻ polyanions
• Electrochemistry
• Fluorescent properties
• Pentanuclear fragment

Additional information

Funding

Funding. This work was supported the National Natural Science Foundation of China [grant number 21271056] and [grant number 21371042]; the Ministry of Education and Specialized Research Fund for the Doctoral Program of Higher Education [grant number 20122329110001]; the Natural Science Foundation of Heilongjiang Province [grant number B201216], Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, Doctoral initiation Foundation of Harbin Normal University [grant number KGB201214]; Program for Scientific and Technological Innovation Team Construction in Universities of Heilongjiang Province [grant number 2011TD010].