While reactions between ions and neutral molecules in the gas phase have been studied extensively, reactions between molecular ions of same polarity remain relatively unexplored. Herein we show that reactions between fragment ions generated in the gas phase and molecular ions of the same polarity are possible by soft‐landing of both reagents on surfaces. The reactive [B 12 I 11 ] 1− anion was deposited on a surface layer built up by landing the generally unreactive [B 12 I 12 ] 2− . Ex‐situ analysis of the generated material shows that [B 24 I 23 ] 3− was formed. A computational study shows that the product is metastable in the gas phase, but a charge‐balanced environment of a grounded surface may stabilize the triply charged product, as suggested by model calculations. This opens new opportunities for the generation of highly charged clusters using unconventional building blocks from the gas phase.

In this work, we present a powerful synthetic strategy for selectively converting phosphole oxides by reaction with sulfonyl isocyanates into the corresponding sulfonylimino phospholes, which show a decrease or increase in solid-state emission.

Polyoxovanadate anions immobilized on conducting substrates are promising candidates for molecule-based memory technologies. However, strong electronic interactions with the substrate and the formation of larger agglomerates remain bottlenecks on the way to their technical application. We demonstrate that ion soft-landing of mass selected cyclodextrin-functionalized hexavanadates enables deposition of these host–guest complexes as single memory units on surfaces without their quaternary ammonium countercations from solution. Cyclodextrin provides a stabilizing “shell” for the dianions. Multistate switching evidenced by the change in molecular resistance has been detected using scanning tunneling microscopy and spectroscopy and attributed to reduction of individual vanadium (+V) centers.

The synthesis, structure, magnetic, and photophysical properties of two dinuclear, luminescent, mixedligand [Cr III 2 L(O 2 CR)] 3 + complexes (R = CH 3 (1), Ph (2)) of a 24membered binucleating hexa-aza-dithiophenolate macrocycle (L) 2À are presented. X-ray crystallographic analysis reveals an edge-sharing bioctahedral N 3 Cr(μ-SR) 2 (μ 1,3 -O 2 CR)CrN 3 core structure with μ 1,3 -bridging carboxylate groups. A ferromagnetic superexchange interaction between the electron spins of the Cr 3 + ions leads to a high-spin (S = 3) ground state. The coupling constants (J = + 24.2(1) cm À 1 (1), + 34.8(4) cm À 1 (2), H = À 2JS 1 S 2 ) are significantly larger than in related bis-μalkoxido-μ-carboxylato structures. DFT calculations performed on both complexes reproduce both the sign and strength of the exchange interactions found experimentally. Frozen methanol-dichloromethane 1 : 1 solutions of 1 and 2 luminesce at 750 nm when excited into the 4 LMCT state on the 4 A 2 ! 2 T 1 (ν 2 ) bands (λ exc = 405 nm). The absolute quantum yields (Φ L ) for 1 and 2 were found to be strongly temperature dependent. At 77 K in frozen MeOH/CH 2 Cl 2 glasses, Φ L = 0.44 � 0.02 (for 1), Φ L = 0.45 � 0.02 (for 2).

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