Solvothermal Synthesis, Crystal Structures, and Photocatalytic Properties of Iodoplumbate Hybrids with Nickel(II) Complex Templates

Abstract

Organic–inorganic iodoplumbate hybrids [Ni(en)2]2Pb3I10 (1), [Ni(en)3]Pb2I6 (2) (en = ethylenediamine), [Ni(dien)2]Pb2I6·H2O (3) (dien = diethylenetriamine), [Ni(14‐TMC)][PbI3]2·DMF (4), and [Ni(14‐TMC)]2[Pb5I14(DMSO)2] (5) (14‐TMC = 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane) were prepared using different NiII complex cation as structural directing agents under solvothermal conditions. Compounds 1–4 consist of 1‐D [Pb3I104–]n, [PbI3–]n and [Pb2I62–]n polymeric anions constructed by PbI6 octahedra via corner‐, edge‐ or face‐sharing, respectively. The novel organic hybrid iodoplumbate anion [Pb5I14(DMSO)24–]n in 5 is composed of PbI6 and PbI5O octahedra via edge‐ and face‐sharing. The formation of polymeric iodoplumbate anions in 1–5 indicates different structure‐directing effect of the NiII complex cations with various polyamino ligands under appropriate reaction and crystallization conditions. Compounds 1–5 exhibit tunable band gaps varying in the range of 2.18–2.61 eV. Compounds 4 and 5 are more effective than 1 and 3 in the photocatalytic degradation of methylene blue.

Two New Hybrid Iodoplumbates with Chain-like Cations

“…It can be seen that the optical absorption edges of compounds 1 and 2 are estimated to be 2.50 and 2. 7,12,13,18,19,30 In addition, we also noted that compound 1 exhibits an obvious blue shift with respect to that of bulk PbI 2 (2.30 eV). 30 This result was normal and also found in some documented iodoplumbate compounds (e.g., [Ni(en) 3 ]Pb 2 I 6 , [Co-(phen) 3 ] 2 Pb 3 Cu 6 I 16 •C 2 H 5 OH, and [Fe(en) 3 ]Pb 2 I 6 )), which may provide a new approach to tune the band gaps for presynthesized materials.…”

“…30 This result was normal and also found in some documented iodoplumbate compounds (e.g., [Ni(en) 3 ]Pb 2 I 6 , [Co-(phen) 3 ] 2 Pb 3 Cu 6 I 16 •C 2 H 5 OH, and [Fe(en) 3 ]Pb 2 I 6 )), which may provide a new approach to tune the band gaps for presynthesized materials. 18,19,30 Photoelectric Performances. To further probe the semiconducting natures of the title compounds, we also investigated their photoelectric switching properties.…”

“…So far, a large number of iodoplumbate hybrids with various templating cations and structural dimensions based on the above-mentioned SBUs have been solvothermally synthesized and structurally characterized. For instance, 0D [Pb 5 I 16 ] 6– , 0D [Pb 18 I 44 ] 8– , 1D [PbI 3 ] n n – , 1D [Pb 7 I 24 ] n 10 n – , 1D [Pb 3 I 10 ] n 4 n – , 2D [Pb 7 I 18 ] n 4 n – , 2D [PbI 4 ] n 2 n – , 2D [Pb 3 I 9 ] n 3 n – , 2D [Pb 3 I 8 ] n 2 n – , 3D [Pb 8 I 21 ] n 5 n – , and 3D [Pb 4 I 10 ] n 2 n – . ,− Noteworthy is that, among them, the compounds containing organic monoamines/polyamines, nitrogen-containing organic ligands, metal-aliphatic amine complexes, and metal-conjugated organic ligand complexes have been well documented. − ,− ,− Comparatively speaking, the examples decorated by carboxylic acid-type organic ligands are rarely isolated. In fact, in addition to iodine, the Pb 2+ ion was also easy to bond with oxygen, showing diversified coordination modes to the carboxylic acid group. ,− Their introduction not only may endow the as-prepared compounds with rich structural types but also may induce fascinating chemical or physical performances. ,− For example, compound [(CH 3 ) 2 NH 2 ] 3 ­Pb 2 I 3 (BDC) 2 (H 2 BDC = 1,4-benzenedicarboxylic acid) displays interesting dual-emission properties inherited from the synergistic contributions of BDC 2– ligands and [PbI 3 O 4 ] n 9 n – moieties …”

Structural Diversity in 2,2′-[Naphthalene-1,8:4,5-bis(dicarboximide)-N,N′-diyl]-bis(ethylammonium) Iodoplumbates

“…The wires contain three crystallographically distinct lead environments–two types of PbI 6 octahedra and PbI 5 (DMF) octahedra–in a 1:2:2 ratio. PbI 5 (DMF) octahedra have previously been reported in the structures of [(Pr 3 NC 2 H 4 NPr 3 )­Pb 6 I 14 (DMF) 2 ]·4DMF, [(Ph 4 P) 4 Pb 15 I 34 (DMF) 6 ], and [PbI 2 (DMF)]. − Other solvent molecules, such as dimethyl sulfoxide (DMSO), have also been found to replace iodide ions in the coordination sphere of Pb. − In the present structure, the main chain is defined by the two types of PbI 6 octahedra, with the PbI 5 (DMF) octahedra fused to the sides of the chains. The first of the two types of PbI 6 octahedra shares two of its faces with PbI 6 octahedra of the second type, while two of its vertices are also shared with two PbI 5 (DMF) units.…”

Heterometallic Pb–Ag Iodides from 1‐D Chains to 2‐D Layers Induced by Transition Metal Complex Cations: Syntheses, Crystal Structures, and Photocatalytic Properties

“…The Ni-N bond lengths and N-Ni-N bond angles are comparable to those observed in the compound containing the [Ni(en) 2 ] 2+ complex unit. [18] The [PbAg 2 I 6 ] asymmetric unit of compound 4 contains two crystallographically independent Ag, one Pb and six I atoms (Figure 2b). Both Ag(1) + and Ag(2) + ions are coordinated to four iodine anions at distances in the range of 2.804(4)-3.016(4) Å (Table S1).…”