Syntheses, Crystal Structures, and Photocatalytic Properties of Bromoargentates Induced by Transition‐Metal–phen Complex Cations

Abstract

The bromoargentates [TM(phen) 3 ] 2 Ag 13 Br 17 ·2dmso·-3H 2 O [TM = Fe (1), Co (2), Ni (3)], [Cu(phen) 2 (Br)]AgBr 2 (4), [Fe(phen) 3 ]Ag 2 Br 4 ·dmf (5), and [Fe(phen) 2 (Cl) 2 ] 2 Ag 2 Br 4 (6) (phen = 1,10-phenanthroline) were prepared by the reactions of AgBr, KBr, and phen with transition-metal salts in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF) solvent. In 1-3, AgBr 4 tetrahedra form [Ag 7 Br 13 ] secondary building units (SBUs) through edge sharing. The [Ag 7 Br 13 ] SBUs interconnected by face sharing form polymeric [Ag 13 Br 17 4-] n anions with a 3D structure, and this is the first example of a 3D framework of bromoargentates. The [Ag 13 Br 17 4-] n anion contains interpenetrating channels, in which the [TM(phen) 3 ] 2+ (TM = Fe, Co, Ni) [a] College

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

“…Therefore, the introduction of TM complex cations can improve the photoelectronic properties of hybrid iodoargentates, and great efforts have been put into the synthesis of functional hybrid iodoargentates such as the TM-complex-containing iodoargentates (Table S1). ,,,− However, the controlled synthesis of hybrid iodoargentates remains a challenge because of the influence of external stimuli (e.g., reaction temperature, solvent, and pH value) upon the structures and dimensions of iodoargentates during the crystallization process. ,− In spite of the synthesis and structural characterization of numerous hybrid iodoargentates, systematic research on these external factors has not been explored. Recent research has demonstrated that it is easy to obtain low-dimensional iodoargentates at a lower temperature (Table S1).…”

“…Recent research has demonstrated that it is easy to obtain low-dimensional iodoargentates at a lower temperature (Table S1). ,,, In this research, we systematically studied the hybrid iodoargentates directed by TM-complexed cations at a lower temperature. We synthesized three types of low-dimensional iodoargentate hybrids, [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 )), with distinct characteristics of semiconductors and photocatalytic activities.…”

“…Recent research has demonstrated that it is easy to obtain low-dimensional iodoargentates at a lower temperature (Table S1). 37,39,42,43 In this research, we systematically studied the hybrid iodoargentates directed by TM-complexed cations at a lower temperature. We synthesized three types of low-dimensional iodoargentate hybrids, [TM(phen…”

Polymeric Iodoargentate Hybrids Incorporating Octakis- or Heptakis-Solvated Lanthanide Complexes: Syntheses, Crystal Structures, and Photocatalysis

“…15 Recently, we found that the TM−bromoargentate hybrids [Cu(phen) 2 (Br)]AgBr 2 and [Fe(phen) 2 (Cl) 2 ] 2 Ag 2 Br 4 , which consist of 1-D [AgBr 2 − ] n chains and the mix-coordinated [Cu(phen) 2 (Br)] 2+ or [Fe(phen) 2 (Cl) 2 ] + complex, exhibit higher catalytic activities in the degradation of CV than compound [Fe(phen) 4− ] n framework. 16 The photocatalytic activities of the haloargentate hybrids are related to many influencing factors, such as structural differences of the anionic haloargentate clusters and an assortment of their antications as well as the electron-accepting ability of the antications. 11c,15 In the past decade, the lanthanide complex cation has been used as a structure-directing agent (SDA) to synthesize iodoargentate hybrids containing Ln components.…”

“…The 2-D iodoargentate [Cu­(phen) 3 ] 2 Ag 11 I 15 ·H 2 O is more active than the 3-D iodoargentates [M­(phen) 3 ] 2 Ag 13 I 17 (M = Co, Cd; phen = 1,10-phenanthroline) in the photodegradation of RhB . Recently, we found that the TM–bromoargentate hybrids [Cu­(phen) 2 (Br)]­AgBr 2 and [Fe­(phen) 2 (Cl) 2 ] 2 Ag 2 Br 4 , which consist of 1-D [AgBr 2 – ] n chains and the mix-coordinated [Cu­(phen) 2 (Br)] 2+ or [Fe­(phen) 2 (Cl) 2 ] + complex, exhibit higher catalytic activities in the degradation of CV than compound [Fe­(phen) 3 ] 2 Ag 13 Br 17 ·2DMSO·3H 2 O containing the 3-D [Ag 13 Br 17 4– ] n framework . The photocatalytic activities of the haloargentate hybrids are related to many influencing factors, such as structural differences of the anionic haloargentate clusters and an assortment of their antications as well as the electron-accepting ability of the antications. , …”