Novel Anderson-type [TeMoO]-based metal-organic complexes tuned by different species and their coordination modes: assembly, various architectures and properties

Four novel Anderson-type polyoxometalates (POMs) [TeMo 6 O 24 ] 6− (TeMo 6 )-based metal-organic complexes (MOCs), namely, H 2 [Zn 4 (3-Hdpyp) 2 (TeMo 6 O 24 ) 2 (H 2 O) 16 ]·6H 2 O ( 1 ), [Zn 3 (3-dpyb) 2 (TeMo 6 O 24 )(H 2 O) 12 ]·8H 2 O ( 2 ), [Cu 2 (4-Hdpyp) 2 (TeMo 6 O 24 )(H 2 O) 6 ]·4H 2 O ( 3 ), and [Cu 3 (3-dpyp) 2 (TeMo 6 O 24 )(H 2 O) 8 ]·4H 2 O ( 4 ) (3-dpyp = N , N ′-bis(3-pyridinecarboxamide)-1,3-propane, 3-dpyb = N , N ′-bis(3-pyridinecarboxamide)-1,4-butane, 4-dpyp = N , N ′-bis(4-pyridinecarboxamide)-1,3-propane), were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). In complex 1 , two TeMo 6 polyoxoanions bridge Zn II ions to generate a discrete tetranuclear zinc complex H 2 [Zn 4 (3-Hdpyp) 2 (TeMo 6 O 24 ) 2 (H 2 O) 16 ]. In 2 , the TeMo 6 anions connect the metal-organic units [Zn 3 (3-dpyb) 2 ] 6+ to form an Anderson-type TeMo 6 -based wave-like metal-organic chain. Both the discrete tetranuclear subunits in 1 and 1D wavy chains in 2 were further extended to 2D supramolecular networks through the hydrogen bonding interactions. In complex 3 , the TeMo 6 anions link the metal-organic units [Cu 2 (4-Hdpyp) 2 ] 6+ to construct a 2D layer, which is further extended to a 3D supramolecular framework by the hydrogen bonding interactions. In complex 4 , the TeMo 6 polyoxoanions bridge the Cu II ions to generate a 2D Cu-TeMo 6 inorganic layer, which is further linked by the μ 2 -bridging 3-dpyp ligands to form a 3D metal-organic framework. The effects of various coordination modes of TeMo 6 polyanions and the bis-pyridyl-bis-amide ligands, as well as the central metals on the structures of the title complexes have been discussed. Besides, the fluorescence, electrochemical properties and photocatalytic activities of the title complexes have been investigated in detail. Four novel Anderson-type polyoxometalate [TeMo 6 O 24 ] 6− -based metal-organic complexes were hydrothermally synthesized and characterized, which show fluorescence, electrochemical and photocatalytic properties.