RESUMO
Two thiacalix[4]arene-protected silver(I) alkynyl nanoclusters, [Na2(H2O)2][Ag9(TC4A)(tBuCîC)4(CH3OH)2(SbF6)0.5(OH)2.5]·3.5H2O·CH3OH (1, abbreviated as Ag9) and [Ag9(TC4A)(tBuCîC)4(CF3COO)]2·4CH3OH (2, abbreviated as Ag18), were synthesized by the reaction of [tBuCîCAg]n, p-tert-butylthiacalix[4]arene (H4TC4A), NaBH4, and AgSbF6 or CF3COOAg in the mixed solvent of methanol-trichloromethane-toluene under solvothermal conditions, respectively. Driven by SbF6- and CF3COO- with different coordination properties, the structural unit [Ag9(TC4A)(tBuCîC)4]+ in both the compounds migrated in different modes, accompanied by distinct Agâ¯Ag distances. Ag9 and Ag18 exhibit similar UV-Vis absorption and diffuse reflection spectra along with contrary tendency between photocurrent responses and solid-state fluorescence. The solution stability of Ag9 and Ag18 was demonstrated by 1H NMR and MALDI-TOF mass spectrometry. The fluorescence responses of Ag9 and Ag18 towards different organic molecules were also investigated, which indicated that the polarity of solvent has a certain effect on the emission intensities of Ag9 and Ag18. This study provides a positive guide for the controlled synthesis and further study of the structure-activity relationship of thiacalix[4]arene-protected silver alkynyl nanoclusters.
RESUMO
Structural transformation is important for the study of silver cluster compounds, in which controlled synthesis of their shapes and sizes via anion template-driven is one key scientific question. In this work, the CO3 2- anion templates were captured by the [t BuC≡CAg]n system under the stimulation induced by carboxylate ligand CF3 COO- /PhCOO- , and two silver alkynyl clusters [(CO3 2- )@Ag21 (t BuC≡C)16 (CF3 COO)3 (H2 O)]â DMFâ 2CH2 Cl2 (1) and [(CO3 2- )2 @Ag24 (t BuC≡C)16 (PhCOO)4 ]â CH3 OHâ 4DMF (2) have been successfully isolated and charactered. With the increase of the number of CO3 2- templates from single to double, the outer silver atoms from twenty-one to twenty-four, accompanied by the growth of the cluster skeleton from 9.8â Å ×6.9â Å of the (CO3 2- )@Ag21 unit to 10.5â Å ×7.3â Å of the (CO3 2- )2 @Ag24 unit. In addition, the syntheses, structures, photocurrent responses, cyclic voltammetry characteristics, luminescence, and photodegradation of compounds 1 and 2 have been studied.
RESUMO
Compound [Ag44 (W10 O32 )(St Bu)24 (CF3 COO)8 ](CF3 COO)6 â 6H2 O (1) was synthesized through a one-pot method. This is the first case of isolating a new silver thiolate cluster containing a [W10 O32 ]6- template which transforms from WO4 2- polyoxoanion through a self-assembly process. The anionic nature of the reduced [W10 O32 ]6- template and the effective silver-oxygen interaction contribute to the formation of the Ag44 nanowheel in 1. The luminescence, photocatalytic activity and electrochemistry properties of 1 were studied.
Assuntos
Luminescência , Prata , Ânions , Prata/químicaRESUMO
The remarkably reversible thermochromic luminescence behavior and the rare nonlinear optical (NLO) properties of the [Ag55(MoO4)6(C[triple bond, length as m-dash]C t Bu)24(CH3COO)18(CH3COO)]·2H2O ({Ag55Mo6} for short) nanocluster reported were investigated experimentally. The important contributions of Ag+, C[triple bond, length as m-dash]C- ions and MoO4 2- groups to the NLO properties were proved by further density functional theory (DFT) calculations.
RESUMO
A high-yield silver alkynyl assembly [Ag8(C[triple bond, length as m-dash]C t Bu)5(CF3COO)3(CH3CN)] n (1) constructed from [AgC[triple bond, length as m-dash]C t Bu] n ligand, CF3COOAg and CH3CN auxiliary ligands with a one-dimensional infinite chain structure has been obtained in one pot. Compound 1 has been well-defined and characterized. The photocurrent properties and the temperature-sensitive luminescent properties of 1 have been investigated.
RESUMO
Compound [Ag42 S5 (StBu)25 (CF3 COO)4 (CO3 )](CO3 )0.5 â CH2 Cl2 â 4CH3 OHâ 9DMF (1) has been obtained and well defined. It consists of a multi-shell structure involving two Ag centres, one Ag5 S5 pentagram, two Ag5 S5 pentagons and one Ag25 S15 shell. Compound 1 has been characterized by XPS, FT-IR, PXRD, TGA, NMR, MS, UV/Vis spectrum, TEM and cyclic voltammetry. Temperature-sensitive luminescent property of 1 has also been investigated.