Sequential Self-Organization of Silver(I) Layered Materials with Strong SHG by J Aggregation and Intercalation of Organic Nonlinear Optical Chromophores through Mechanochemical Synthesis

Abstract

The inorganic−organic hybrid layered material of stoichiometry [DAMS+][Ag5I6 -], characterized by a strong SHG activity, has been prepared mechanochemically by room-temperature ball-milling a mixture of AgI and [DAMS+][I-], eventually followed by a moderate heating. By means of electronic absorption spectra, XRPD, and second harmonic generation (SHG) experiments we proved that the intralayer ordering of the [DAMS+] nonlinear optical chromophores into J-aggregates precedes the interlayer one, on the whole producing, by a sequential process, the “macropolarity” responsible for the strong SHG. The mechanochemical approach was shown to be of general use, as it was successfully applied to the synthesis of the analogous [DAMS+][Cu5I6 -], [DAZOP+][Ag5I6 -], and [DAES+][Ag5I6 -] materials.

Quaternary Phosphorus‐Induced Iodocuprate(I)‐Based Hybrids: Water Stabilities, Tunable Luminescence and Photocurrent Responses

“…Structure of (PPh 3 i Pr) 2 (Cu 2 I 4 ) (3): 3 has been previously structurally determined, whose planar (Cu 2 I 4 ) 2– dimer is constructed from two edge‐sharing CuI 3 triangles . The Cu–I lengths and I–Cu–I angles are consistent with those found in other iodocuprates, and the Cu ··· Cu distance of 2.9380(11) Å is somewhat longer than reported iodocuprates . Specially, there are three kinds of C–H ··· π interactions between adjacent PPh 3 i Pr + cations (Table S4).…”

Cu(I) hybrid inorganic–organic materials with intriguing stimuli responsive and optoelectronic properties

“…[154]). The compound was prepared by either solution or solid mixing [155] of [DAMS]I and Cu(I), and, despite the impossibility to grow suitable single crystals for diffraction analysis, its structure was solved by means of XRPD. The structural pattern consists of polymeric CuI slabs stacked along the trigonal axis (Figure 30), which are formed by two parallel, slightly corrugated sheets.…”

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

“…Organic–inorganic hybrid halometalates are of great interest owing to their wide range of structural diversity, potential applications in optical and electrical materials, and phase transitions . Among metal halide hybrids, silver(I) halide hybrid materials have attracted much attention because of their rich structural topologies and interesting physical properties, which include optical and semiconducting properties and photocatalysis . The rich structural diversity of silver(I) halides is believed to be based on the strong affinity of Ag I for halogen atoms and the various coordination modes of halogen atoms.…”

“…To date, a large number of silver(I) iodine [Ag m I n ] ( n – m )– anions ranging from discrete clusters (0D) to one‐dimensional (1D) chains, two‐dimensional (2D) layers, and three‐dimensional (3D) frameworks have been reported and characterized. Examples of iodoargentate anions include the 0D clusters [Ag 4 I 8 ] 4– , [Ag 14 I 16 ] 2– , and [Ag 14 I 22 ] 8– ; the 1D chains [Ag 2 I 3 ] – , [Ag 2 I 4 ] 2– , [Ag 3 I 5 ] 2– , [Ag 4 I 6 ] 2– , [Ag 5 I 7 ] 2– , [Ag 5 I 9 ] 4– , [Ag 6 I 9 ] 3– , and [Ag 11 I 15 ] 4– ; the 2D layers [Ag 2 I 3 ] – , [Ag 4 I 5 ] – , [Ag 5 I 6 ] – , [Ag 6 I 8 ] 2– , and [Ag 6 I 9 ] 3– ;[3c], [15b], and the 3D networks [AgI 2 ] – , [Ag 2 I 4 ] 2– , [Ag 4 I 6 ] 2– , [Ag 5 I 6 ] – , [Ag 5 I 7 ] 2– , [Ag 9 I 13 ] 4– , [Ag 12 I 16 ] 4– , [Ag 13 I 17 ] 4– , and [Ag 14 I 16 ] 2– , . The structures and dimensionalities of iodoargentates are influenced by various factors, including pH value, solvent, and reaction temperature in the synthesis process and structure‐directing agents (SDAs).…”