Transition-Metal-Complex-Directed Synthesis of Hybrid Iodoargentates with Single-Crystal to Single-Crystal Structural Transformation and Photocatalytic Properties

Abstract

We synthesized and characterized three types of isostructural iodoargentates, [TM(phen) 3 ]Ag 2 I 4 •3DMF (TM = Co (1), Ni (2), Zn (3)), [TM(phen) 3 ]Ag 3 I 5 •DMF (TM = Co (4), Ni (5), Zn (6)), and [TM(phen) 3 ] 2 Ag 8 I 12 •7DMF (TM = Co (7), Ni (8), Zn ( 9)) (phen = 1,10-phenanthroline, DMF = dimethylformamide) using transition-metal (TM) complexes as the structuredirecting agents. Compounds 1−3 and compounds 4−6 feature zero-dimensional anionic [Ag 4 I 8 ] 4− and [Ag 6 I 10 ] 4− clusters, respectively. All of the [TM(phen) 3 ] 2+ cations in compounds 1−6 are arranged into a two-dimensional (2D) (6,3) net layer. Interestingly, compounds 1−3 are kinetically unstable in the mother solution, and they can be converted to compounds 4−6 via irreversible single-crystal to single-crystal transformation processes, respectively, with distinct changes in the crystal morphology and structure. Compounds 7−9 feature one-dimensional (1D) zigzag chains constructed from [Ag 8 I 12 ] 4− units. The UV−vis diffuse reflectance measurements demonstrate that compounds 1−9 possess the characteristics of semiconductors with band gaps of 2.58− 2.71 eV and visible-light-irradiation-induced photocatalytic activities. Especially, compound 3 possesses higher photocatalytic degradation activity toward crystal violet (CV) and rhodamine B (RhB) in comparison to P25 under identical conditions. Moreover, the mechanism study reveals that the TM complex cations make a great contribution to the photocatalytic activity.

Assembly of One-, Two-, and Three-Dimensional Cu(I)-Based Coordination Frameworks for Tunable White Light Emission and Effective Fluorescence Sensing

“…Extrapolation of the linear portion of the absorption edge gives the values of band gap ( E g ) for 1 – 3 with 2.34, 2.65, and 2.33 eV, respectively, which correspond to the colors of the solid samples. Comparing with the absorption edges of bulk CuBr (2.89 eV) and CuI (2.95 eV), the hybrid solids feature obvious red-shifted phenomena similar to other metal-halide-based complexes, which can be mainly ascribed to the contribution of organic moieties. − To gain insight into the relationship between optical properties and crystal structures, we have carried out theoretical studies for compound 3 (selected as an example) by using DFT theory to explore its electronic structure. As the optical property is primarily originated from the electronic transition among electronic states near the region of Fermi level, thus the occupied and unoccupied states at the top of valence band (VB) and the bottom of conduction band (CB) have been studied, respectively.…”

Reversible single-crystal-to-single-crystal transition in Gd(iii) metal–organic frameworks induced by heat and solvents with a significant magnetocaloric effect

“…6,7 Ligand substitution is another method, which involves the exchange of substances and the breaking and generation of coordination bonds. 8,9 In addition, the realization of reversible single-crystal-to-single-crystal (SC-SC) conversions and the definite structures determined using X-ray single-crystal diffraction provide the opportunity to study structure-function relationships. This can be extremely relevant through the crystal transformations allowing access to a variety of dynamically switchable physical properties such as magnetism, 10,11 fluorescence, [12][13][14] catalysis, 15 electrical conductivity, [16][17][18] and gas storage.…”

Facile syntheses, structures and photocatalytic properties of 3D iodoargentate frameworks derived from TM-flexible-amino-ligand templates

“…1,8 The counter cations of Ln(III) complexes [LnL 8 ] 3+ (L = DMSO, DMF, DMA) led to the formation of the iodoargentate anions [Ag 6 I 9 ] 3− , [Ag 5 I 8 ] 3− , [Ag 7 I 10 ] 3− , and [Ag 9 I 12 ] 3− with three negative charges, 28,31,32 whereas, the counter cations of TM complexes usually produced the iodoargentate anions with even negative charges. 12,20,22,25 In addition, the structures of the iodoargentate anions were intriguingly affected by the solvent and synthesis methods. The TM(II) complex cations [TM(phen…”