The capricious nature of iodine catenation in I₂ excess, perovskite-derived hybrid Pt(iv) compounds

Abstract

Perovskite-derived hybrid platinum iodides with the general formula A2PtIVI6 (A = formamidinium FA and guanidinium GUA) accommodate excess I2 to yield hydrogen-bond-stabilized compounds where the I2 forms catenates with I− anions on the PtI6 octahedra.

“Anti‐electrostatic” Halogen Bonding between Ions of Like Charge

“…In this crystal structure, I 3 À bridges the PtI 6 2À units, thus forming infinite chains with R XB = 0.88 and ∡ Pt-I-I = 179°(see Figure 10a). [41] Another example is depicted in Figure 10b, showing the self-assembled chain-motif of bis(m 2 -iodo)-tetraiodo-di-tellurium (R XB = 0.92, ∡ Te-I-I = 170°). [42] Polyhalides represent another class of inorganic compounds showing halogen bonding involving anionic counterparts.…”

“…[43] The analogous Br 4 2À also WUJGAM [13] 8 I I À 3.331 0.797 177.5 WUJGIU [13] 8 I Cl À 3.022 0.797 173.6 I Cl À 3.051 0.805 175.2 WUJGOA [13] 8 I I À 3.337 0.806 177.6 I I À 3.416 0.817 171.8 FUWFOV [15] 17 I I À 3.920 0.938 169.0 TUPKIZ [39] 18 Br I À 3.637 0.930 172.4 DISJOE [40] 19 Cl NO 3 À 3.137 0.959 145.9 ). [41] b) Self-assembled chains of bis (triethylhydroxyphosphonium) bis(triethylphosphine oxide) bis(m 2 -iodo)-tetraiodo-di-tellurium (Ref.…”

“…Figure10. a) Infinite halogen bonded chains in the co-crystal between bis (dimethylammonium) hexaiodoplatinum(IV) and dimethylammonium triiodide (CSD-number: 1864903) [41]. b) Self-assembled chains of bis (triethylhydroxyphosphonium) bis(triethylphosphine oxide) bis(m 2 -iodo)-tetraiodo-di-tellurium (Ref.-Code: CEMMEN)[42] (counterions omitted for clarity, purple: iodine, teal: tellurium, grey: platinum).…”

(15‐crown‐5)BiI3 as a Building Block for Halogen Bonded Supramolecular Aggregates

“…Halogen bonding has emerged as an important interaction in supramolecular chemistry, [1] and continues to be of great current interest regarding its theoretical description [2] and in fields of application from catalysis [3] to material science [4] and biochemistry. [5] Metal halide complexes can also be used in the construction of supramolecular aggregates involving halogen bonds, serendipitously or by design when halogenated solvents like halomethanes are used, [6,7] in many polyhalide compounds [8][9][10][11][12][13][14][15] or through addition of typical halogen bond donors like tetraiodoethylene (TIE) or 1,4diiodotetrafluorobenzene. [16][17][18][19] A recent example by the Huber group has also shown that the activation of metal halide bonds through halogen bonding is important in homogeneous catalysis.…”

Ordered B-Site Vacancies in an ABX3 Formate Perovskite

“…14 The particular motivation for developing B-site vacancy chemistry comes from the prospect for exploiting such vacancies to tune B-site oxidation state, promote low-coordination intercalation, and/or amplify anion-anion interactions. 15 Given the recent discovery that B-site cation substitution is straightforwardly achieved in formate perovskites, we were interested to establish whether this family might support B-site vacancies. An obvious strategy is to employ B n+ cations with charges n > 2: since the organic A-site cation is nearly always monovalent, charge balance could be achieved by reducing the B-site occupancy to 2/n.…”