Do alkyl groups on aromatic or aliphatic structure directing agents affect water stabilities and properties of hybrid iodoargentates?. Issue 37 (12th September 2017)

• Record Type: Journal Article
• Authors: Liu, Guang-Ning; Zhang, Xu; Wang, Hong-Mei; Xu, Hong; Wang, Zi-Han; Meng, Xiang-Long; Dong, Ya-Nan; Zhao, Ruo-Yu; Li, Cuncheng
• Is Part Of: Dalton transactions. Volume 46:Issue 37(2017)
• Page Start: 12474
• Page End: 12486
• Publication Date: 2017-09-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt02152f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Do alkyl groups on aromatic triphenylphosphine or aliphatic piperazine cations have a similar effect on the stabilities and properties of hybrid iodoargentates? Abstract : Two types of in situ formed structure directing agents (SDAs) including aromatic triphenylphosphine (PPh3 )- and aliphatic piperazine (H2 pp)-derivative cations were used to synthesize five new hybrid iodoargentates, namely (EtPPh3 )Ag3 I4 (1, Et = ethyl), ( n -PrPPh3 )Ag3 I4 (2, n -Pr = n -propyl), (i-PrPPh3 )Ag5 I6 (3, i-Pr = isopropyl), (Me4 pp)0.5 AgI2 (4, Me = methyl), and (H3 app)2 (Ag2 I6 )·2I·2H2 O (5, app = N -aminoethylpiperazine). A comparative study of the two types of SDAs on the structures, stabilities and properties of hybrid iodoargentates was performed in detail. Structurally, except for (EtPPh3 ) + and ( n -PrPPh3 ) +, which both directly form (Ag3 I4 ) − anionic chains in1 and2, three SDAs generate hybrid iodoargentates different from each other with inorganic anions ranging from a 0-D (Ag2 I6 ) 4− dimer to 1-D α-type (AgI2 ) − and (Ag5 I6 ) − chains. With regard to the electronic structures, aromatic PPh3 -derivative cations make noticeable contributions to the bottom of the conduction bands, while aliphatic pp-derivative cations make nearly no contribution to the frontier orbitals, clearly indicating their different ways to adjust the band gaps. With regard to stability, the decomposition temperatures of1–3 in the range of 324–349 °C are noticeably higher than the values of 217 and 225 °C for4 and5 . Furthermore, 1–4 exhibit good water stabilities, which is ascribed to the alkylation reactions precluding the formation of strong hydrogen bonds between alkylated SDAs and extraneous H2 O molecules. Contrarily, the presence of typical hydrophilic NH2 +, NH + and –NH3 + groups on the protonated (H3 app) 3+ cation makes5 sensitive to water and a hydrolysis reaction occurs to generate a cubic AgI phase. Finally, 1–3 exhibit high photocatalytic efficiencies for the degradation of rhodamine B (RhB) dye in wastewater under visible light. All conclusions obtained here will help a lot in the synthesis of stable functional metal halide-based hybrids.