Controlling the Architecture of Discrete Organotin Sulfide Molecules by Optimization of the Intramolecular Spacer Length

Abstract

Measured approach: Organotin sulfide complexes adopt different structures depending on the length of the intramolecular organic spacer R, as shown by the synthesis of [(RxSn2)2(μ‐S)6] (e.g.; 1) or [Rx4Sn12S20] (2). For [(RxSn2)2(μ‐S)6], three different arrangements of the organic “straps” attached to [Sn4S6] cages are realized for different length ranges of Rx, whereas the longest spacer provokes a complete rearrangement of the inorganic core to form 2. DFT investigations rationalized the experimental findings.

Functionalized Organotin‐Chalcogenide Complexes That Exhibit Defect Heterocubane Scaffolds: Formation, Synthesis, and Characterization

“…[9,10] It has been shown that it is possible to control the assembly of discrete organotin-sulfide moieties by the judicious selection of suitable bifunctional organic spacer groups. [11] However, investigations of the rearrangement of the inorganic core itself have not been implied so far, except for those on the unique formation of noradamantane-type structures [(RGe) 4 E 5 ]. [12] Herein, we report the synthesis and characterization of new organotin-chalcogenide complexes with the general formula [(R F Sn) 3 E 4 Cl] (E = S, Se).…”

Organotin Selenide Clusters and Hybrid Capsules

“…In organotin sulfide chemistry, the formation of molecular capsules required larger spacer molecules to connect the two hydrazine groups of the parent cluster, with a maximum spacer length found with the 1,4‐bis(diazomethyl)benzene and 1,5‐bisnaphthalene‐functionalized groups, which led to the formation of macrocycles . However, in contrast to the reactions of organotin sulfide clusters, the cagelike compounds could not be obtained upon reaction of the “double‐decker”‐shaped [(R 2 Sn) 4 Se 6 ] precursor.…”

“…The structures of the cations in 3 – 5 also conform to the explanation for the ligand arrangement and structural rearrangement of the cluster core in terms of spacer lengths (C=N⋅⋅⋅N=C) . While the spacer length in 3 (4.33 Å) lies within the range for an anti ‐parallel arrangement of the ligands (4–6 Å), the spacer lengths in 4 a , 4 b , and 5 (9.44, 9.71, and 8.52 Å, respectively) are well above the lower limit for bigger capsules or cavitands (8 Å).…”

“…However, three structural motifs have so far been resistant to a transfer to the heavier homologue: 1) a doubly μ‐Se‐bridged dimer of two defect‐heterocubanes, according to the general formula [(RSn) 4 Sn 2 E 10 ], which is a very common motif for E=S; 2) a rugby‐ball‐shaped cluster capsule, previously reported for E=S as [R 3 (Sn 3 S 4 ) 2 ] (R=(CMe 2 CH 2 C(Me)NNH) 2 C 10 H 6 and (CMe 2 CH 2 C(Me)NNHC(O)CH 2 ) 2 C 14 H 20 )); and 3) a macrocyclic cavitand that results from the linkage of two of the latter clusters by a bridging ligand R, previously reported for E=S as [R 4 (Sn 6 S 10 ) 2 ] (R=(CMe 2 CH 2 C(Me)NNH) 2 C 10 H 6 and (CMe 2 CH 2 C(Me)NNH) 2 C 6 H 4 ) …”

“…However,t hree structural motifs have so far been resistant to at ransfert ot he heavierh omologue:1 )a doubly m-Sebridged dimer of two defect-heterocubanes, according to the general formula [(RSn) 4 Sn 2 E 10 ], which is av ery common motif for E = S; [3,[8][9][10][11] 2) ar ugby-ball-shapedc lusterc apsule, previously reportedf or E = Sa s[ R 3 (Sn 3 S 4 ) 2 ]( R = (CMe 2 CH 2 C(Me)NNH) 2 C 10 H 6 and (CMe 2 CH 2 C(Me)NNHC(O)CH 2 ) 2 -C 14 H 20 )); [10][11][12] and 3) am acrocyclicc avitand that results from the linkage of two of the latter clusters by ab ridgingl igand R, previously reportedf or E = Sa s[ R 4 (Sn 6 S 10 ) 2 ]( R = (CMe 2 CH 2 C(Me)NNH) 2 C 10 H 6 and (CMe 2 CH 2 C(Me)NNH) 2 C 6 H 4 ). [11,12] Herein, we report the continuation of the search for suitable organic linkers and reactionc onditions to afford these uncommon molecular clusters. In addition to one smaller organotin selenide complex, which is also included in this report, this approachl ed us to the isolationo ft wo of the three mentioned targeta rchitectures,w hereas the thirdc lustert ype, the quoted macrocycle, remains elusive in organotin selenide chemistry.…”