Dingxian Jia

Binary Cu12S8 cubic cluster compounds [Ni(en)3]2Cu12S8·H2O (1) (en = ethylenediamine), [{Ni(trien)}2(μ-trien)]Cu12S8·bapip (2) (trien = triethylenetetramine, bapip = N,N'-bis(2-aminoethyl)-piperazine), and [{Ni(tepa)}2(μ-tepa)]Cu12S8·H2O (3) (tepa = tetraethylenepentamine) were prepared by one-step solvorthermal reaction using hydrazine and ethylene polyamine as reaction medium. The cubic cluster [Cu12S8]4- is composed of Cu(I) centers and exclusively monosulfido μ3-S ligands with conterions of Ni(II)-polyamine complex cations which were formed in-situ under solvorthermal condition. Compounds 1-3 exhibited rapid photocurrent responses with reproducible current densities in the range of 2.74-7.30 μA·cm-2. They showed effective photocatalytic activities in degradation of methylene blue with degradation rates of 78.4%, 87.4% and 92.7%, respectively.

TM-complex containing oxotellurogermanate hybrids [Zn(en)3]2Ge4Te4O6·H2O (1) (en = ethylenediamine), [Mn(en)(trien)]2Ge4Te4O6 (2) (trien = triethylenetetramine), and [Mn(dien)2]3Ge4Te4O6·(Te4) (3) (dien = diethylenetriamine) were synthesized by one-pot reactions of ZnSO4·7H2O or MnSO4·4H2O, Ge and Te under mild solvothermal conditions in en, en/trien, and dien solvents, respectively. The adamantane-like structure of the anion [Ge4Te4O6]4- with a central adamantanoid Ge4O6 is composed from four GeO3Te tetrahedra sharing the corners with three other similar tetrahedra through μ-O2- bridges. Compounds 1-3 exhibited strong and stable photocurrent responses with reproducible current densities in the range of 0.86-1.12 μA·cm-2. Compounds 2 and 3 showed higher catalytic activities than 1 in the photodegradation of crystal violet with degradation ratios of 95.1 and 92.6% for 2 and 3, respectively.

Lanthanide(III) iodoargentate hybrids [Ln(terpy)(DMSO)₅]Ag₄I₇ (Ln = Sm (1), Eu (2), Tb (3); terpy = 2,2′:6,2″‐terpyridine; DMSO = dimethyl sulfoxide) are prepared by solvothermal method using lanthanide(III) complex cations formed in situ as templates. All Ln³⁺ ions are coordinated by a terpy and five DMSO ligands, forming [Ln(terpy)(DMSO)₅]³⁺ complex cations with bicapped trigonal prismatic geometry. In 1–3, the four AgI₄ tetrahedra are connected with each other via edge sharing forming an asymmetric structural unit Ag₄I₇. Two Ag₄I₇ units are joined via sharing three I atoms to form the octanuclear isolated anion [Ag₈I₁₄]^6‐ with a centrosymmetric structure, which represents a new member of 0D iodoargentate clusters. The iodoargentates 1–3 show strong and durable photocurrent responses with steady current densities in the range of 0.95–1.28 μA·cm⁻². They exhibit efficient catalytic activities in the photodegradation of methylene blue with degradation rates of 89.3%, 90.9%, and 96.8%, respectively, after 75 min of light irradiation.

Ternary Pb-iodocuprate hybrids [TM(en) ₃ ]PbCuI ₅ [TM = Mn (1), Fe (2), Ni (3)] were prepared using TM( ii )-en complexes as SDAs via a one-pot solvothermal reaction. 1 and 2 exhibited higher catalytic activities than 3 in the photodegradation of CV.

[{Cu(phen)}₂(μ-OH)₂(Ag₃Br₅)]_n (1)/g-C₃N₄ composite was prepared by in situ growth under solvothermal conditions. The composite exhibited much higher photocatalytic efficiency than the parents 1 and g-C₃N₄ in the degradation of crystal violet.

Tellurostannates are traditionally prepared by multistep reactions using the tellurides SnTe, SnTe₂, K₄SnTe₄, or A₆SnTe₆ (A = K, Rb, or Cs) as precursors, which are usually prepared by the molten reaction of alkali metals Sn and Te under harsh synthetic conditions. Differently, ternary Hg–tellurostannate hybrids [Mn(en)₃]HgSnTe₃(Te₂) (1) (en = ethylenediamine), [Mn(dien)₂]HgSnTe₃(Te₂) (2), and [Fe(dien)₂]HgSnTe₃(Te₂) (3) (dien = diethylenetriamine) were synthesized by one-pot reactions using Sn and Te powders as starting materials in the presence of hydrazine under mild solvothermal conditions. In 1, HgTe₃ and SnTe₄ units are joined via Te-sharing to form a 1-D polymeric chain [HgSnTe₃(Te₂)]_n^2n–, while the [HgSnTe₃(Te₂)]_n^2n– chains in 2 and 3 are composed of HgTe₄ and SnTe₄ units. The common feature of the [HgSnTe₃(Te₂)^2–]_n chains in 1–3 is that they are constructed by both the telluride anion Te^2– and the polytelluride anion Te₂^2–. 1–3 exhibited strong photocurrent responses with current densities of 5.26, 3.38, and 3.94 μA cm^–2, respectively. They showed effective photocatalytic activities for methylene blue degradation with degradation ratios in the range of 85.3–94.6% after light irradiation for 80 min. Investigation of the photocatalytic mechanism showed that ^•O₂^– radicals and h⁺ holes were the main active substances in the photodegradation.

3D iodoargentates [Co(en)₃(Ag₂I₄)]_n (1), [Fe(en)₃(Ag₂I₄)]_n (2) and [Co(dien)₂(Ag₂I₄)]_n·nH₂O (3) were prepared by solvothermal methods. Compounds 1–3 were catalytic activity for photodegradation of crystal violet under visible light irradiation.