Four dinuclear organotin halides of composition X n ­Ph(3–n)­Sn­CH2Si­(Me)2–​C12H8–​Si­(Me)2­CH2­SnPh(3–n)­X n (X = Cl, I; n = 1, 2) were prepared and combined in 1:1 stoichiometric reactions with potassium 2,5-pyridinedicarboxylate, 3,5-pyridinedicarboxylate, and piperazine bis-dithiocarbamate, respectively. The reactions yielded a total of five [1 + 1] aggregates with either 21- or 22-membered macrocyclic structures that were fully characterized by elemental analysis, mass spectrometry, IR and NMR (1H, 13C, 29Si, and 119Sn) spectroscopy, and, in three cases, additionally by single-crystal X-ray diffraction analysis. In solution, the macrocycles exhibit conformational and configurational equilibria being fast on the NMR time scale, which, for one of the macrocycles, were closer examined by variable temperature NMR spectroscopy and DFT calculations.

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Hydrolysis reactions of di-and trinuclear organotin halides yielded large novel cage compounds containing SnÀ OÀ Sn bridges. The molecular structures of two octanuclear tetraorganodistannoxanes showing double-ladder motifs, viz., [{Me 3 SiCH 2 (Cl)SnCH 2 YCH 2 Sn(OH)CH 2 SiMe 3 } 2 (μ-O) 2 ] 2 [1, Y = p-(Me) 2 SiC 6 H 4 -C 6 H 4 Si(Me) 2 ] and [{Me 3 SiCH 2 (I) SnCH 2 YCH 2 Sn(OH)CH 2 SiMe 3 } 2 (μ-O) 2 ] 2 •0.48 I 2 [2•0.48 I 2 , Y = p-(Me) 2 SiC 6 H 4 -C 6 H 4 Si(Me) 2 ], and the hexanuclear cage-compound 1,3,6-C 6 H 3 (p-C 6 H 4 Si(Me) 2 CH 2 Sn(R) 2 OSn (R) 2 CH 2 Si(Me) 2 C 6 H 4 -p) 3 C 6 H 3 -1,3,6 (3, R = CH 2 SiMe 3 ) are reported. Of these, the co-crystal 2•0.48 I 2 exhibits the largest spacing of 16.7 Å reported to date for distannoxane-based double ladders. DFT calculations for the hexanuclear cage and a related octanuclear congener accompany the experimental work.

Six dinuclear organotin building blocks of general composition RR'R''SnCH 2 Si(CH 3 ) 2 À biphenylÀ Si(CH 3 ) 2 CH 2 SnR''R'R, in which the tin atoms are separated by a p,p'-biphenylene bridge and carry different substituents [

In a cooperative effort between research groups from Dortmund (Germany, coat of arms on the left) and Cuernavaca (Morelos, México, coat of arms on the right), novel molecular cages were synthesized and characterized by state‐of‐the‐art analytical methods and DFT calculations. Among these novel compounds, the spacer‐bridged tetraorganodistannoxane in the centre showing a double‐ladder structure exhibits a record spacing between the opposite tin centres. More information can be found in the Communication by K. Jurkschat, H. Höpfl, et al. (DOI: 10.1002/chem.202101055).