In Situ Synthesis and Applications for Polyinterhalides Based on BrCl

Abstract

The use of neat BrCl in organic and inorganic chemistry is limited due to its gaseous aggregate state and especially its decomposition into Cl 2 andB r 2 .T he stabilization of BrCl in form of reactive ionic liquidsv ia an ovel in situ synthesis route shifts this equilibrium drastically to the BrCl side, which leads to safer and easier-to-handle interha-logenation reagents. Furthermore, the crystallined erivatives of the hitherto unknown [Cl(BrCl) 2 ] À and [Cl(BrCl) 4 ] À anions were synthesized and characterized by single-crystal X-ray diffraction (XRD), Ramana nd IR spectroscopy,a sw ell as quantum chemical calculations.

The Bromine‐Chlorine Interhalides [Br3Cl5]2–, [Br4Cl4]2– and [Br6.56Cl1.44]2–

“…Interestingly, the Cl atom in the pentahalide is within 2.70–2.92 Å of three Br 2 units. These bonds are only slightly longer than the Cl–BrCl distances in [Cl(BrCl) 3 ] – of 2.60–2.80 Å,, despite the larger σ hole on BrCl compared to Br 2 .…”

From Missing Links to New Records: A Series of Novel Polychlorine Anions

“…Two isostructural compounds, [NPr 4 ][Cl(BrCl) 4 ] [18] and [NPr 4 ][Br(Br 2 ) 4 ] [19] , are known in the literature. When the structures of the polyhalogen anions are compared it can be seen that the distortion of the tetrahedra is most pronounced for the [Cl(Cl) 4 ] − anion (bond angles of 93.2(1)° and 152.6(1)°, compared to 100.3(1)°, 130.1(1)° for [Cl(BrCl) 4 ] − and 99.8(1)°, 131.2(1)° for [Br(Br 2 ) 4 ] − ).…”

A High Energy Density Bromine-Based Flow Battery with Two-Electron Transfer

“…Typical polybromide signals such as Br 3 – and Br 5 – with stretch-mode at about 160 and 260 cm –1 were detected at the state of charge (SOC) lower than 50%, which indicates Br – /Br 2 reactions play a main role in the first plateau . When the SOC exceeded 50%, peaks of polybromides disappeared and an obvious shift to 280 cm –1 could be observed, which correspond to the symmetric stretch-mode of the linear BrCl 2 – anion . The results indicate that the BrCl 2 – /Br 2 reaction is the main mechanism in the second plateau.…”

“…It is worth noting that BrCl 2 – can be further oxidized and a higher capacity can be obtained (Figure S18). The oxidation product structure of BrCl 2 – is complicated, and a longer chain-like structure may be formed with the Cl at a higher oxidation state, such as [Cl­(BrCl) n ] − ( n > 1). ,, Their structure was complex and unstable compared with that of BrCl 2 – , which led to a lower CE (92.5%) and VE (71.9%). Besides, its charging process does not display a distinct voltage step from that of BrCl 2 – .…”