Mixed Cu(i)/Au(i) coordination polymers as reversible turn-on vapoluminescent sensors for volatile thioethers

Abstract

Vapour-phase thioethers play an important role in a wide number of fields, including plant biology, chemical weapon disposal, and brewing but few sensor materials are known. The emissive coordination polymer CuAuCN does not react with vapour phase dimethyl sulphide (DMS) or diethyl sulphide (DES) despite the independent synthesis of emissive [CuAuCN](DMS) and [CuAuCN](DES) from their constituent components in solution. However, the doped CuAuCN rapidly reacts in the solid state with both of these vapour phase thioethers reversibly, with a change in emission from 380/560 nm to 460 nm (DMS) or 420 nm (DES), illustrating that doping the inactive parent CuAuCN with Cu(i) generates an active sensor material. This response can be thermally cycled with little to no loss in functionality. [CuAuCN](DMS), [CuAuCN](DMS), and [CuAuCN](DES) were structurally characterized as 3-D network structures supported by aurophilic interactions.

Control of Structures and Emission Properties of (CuI)n 2-Methyldithiane Coordination Polymers

“…CP1 and CP2 are found non-emissive, which corroborates the trend observed in the literature. 11 However, the unprecedented motif of the Cu 8 I 8 SBU urged for a detail study of the emission properties (Figure 8). Moreover, the photophysical properties of CP3 (Table 2) were also compared to those for the 0D cluster Cu 8 I 8 (S(i-Pr) 2 ) 6 60 and the CPs [Cu 8 I 8 (p- S14) and exhibits a strong emission band at 534 nm which red-shifts to 574 nm upon going from 298 to 77 K (Figure 8).…”

“…The design of coordination polymers with a predictable secondary building unit (SBU) and dimensionality is a quasi-impossible task but the quest remains of great interest for the discovery of new materials with desired properties such as gas adsorption, [1][2][3][4][5][6][7][8][9] sensing, [10][11][12][13][14][15] thermochromism, [16][17][18][19] magnetism, [20][21][22][23][24] conductivity, [25][26][27][28] redox-activity, 29,30 catalysis, 13,[31][32][33] nonlinear optical behavior 34,35 and luminescence. 8,[36][37][38][39][40] Recent reviews on CPs formed by mono-and dithioethers with CuX salts (X = Cl, Br, I) [41][42][43][44][45][46]…”

Two-way vapochromism of a luminescent platinum(ii) complex with phosphonic-acid-functionalized bipyridine ligand

“…Other promising approaches recently developed involve the use of host-guest interactions between the adsorbing material and vapour molecules [23][24][25][26][27][28] or the use of ligand substitution reactions at metal centres. [29][30][31][32][33][34][35][36][37] Most of the vapochromic behaviour reported so far is essentially based on the colour differences between vapouradsorbed and vapour-released phases. Although many vapochromic materials have been reported to date, there are few examples that exhibit switching vapochromic behaviour.…”

Zinc Tetracyanoplatinate: A Reversible Luminescence‐Based Ammonia Sensor

“…Samples were drop‐cast onto a glass slide from a suspension in EtOH. Time‐resolved responses to concentrated ammonia were measured by placing the slide inside a vented cuvette and bubbling air through an aqueous 27–30 % NH 4 OH solution and into the cuvette (using the same apparatus described previously) . For low flow rate ammonia vapor exposures, air was bubbled through the vial of 27–30 % NH 4 OH by using a syringe manually to bubble 10 mL of air through the vial over a 2 minute period.…”

“…Cyanometallate‐containing coordination polymers make excellent candidates for chemical vapor sensors, since they are robust and there are many examples of vapochromic and vapoluminescent species . Many of these utilize cyanometallates with close d 10 –d 10 or d 8 –d 8 metal distances (especially between Au I or Pt II centers)—referred to as being metallophilic—since such materials often display emissive behavior . In addition, the ν CN stretching frequency in metal cyanides is very intense when observed by IR or Raman, and provides an excellent vibrational spectroscopy handle that can also be exploited for sensing applications.…”