Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)₄S₆], [(RSn)₃S₄]²⁻, [(RT)₂(CuPPh₃)₆S₆], and [(RSn)₆(OMe)₆Cu₂S₆]⁴⁻ (R=C₂H₄COOH, CMe₂CH₂COMe; T=Ge, Sn)

Abstract

A series of compounds comprising functionalized thiometallate cages [(RT)4S6] (R terminated by COO(H) or COR groups), based on adamantane (T=Ge) or double-decker (T=Sn) type structures or [(RSn)3S4]2- anionic defect heterocubanes were synthesized and their reactions with 1) transition-metal compounds and 2) hydrazine derivatives were explored. Hence it was possible to generate functionalized ternary CuSnS or CuGeS clusters and to transfer COR ligands into CR(N-NH2) or CR(N-NHPh) terminal groups, respectively. The report provides the proof-of-principle for a directed functionalization and derivatization of chalcogenidometallate cages with respect to the formation of chalcogenidometallate-organic hybrid compounds containing M/E semiconductor nodes, as an alternative to the so far most prominent M/O combination in metal-organic frameworks. DFT investigations deliver further insight in the peculiarities of Ge/S versus Sn/S precursors and their products.

Ternary Mixed‐Valence Organotin Copper Selenide Clusters

“…[23][24][25][26][27] The elemental combination Cu/Sn/ E, for instance, is currently actively studied regarding molecular multi-componentp recursors for highly efficient copper-zinctin-sulfide/selenide (CZTS/Se) solar cells. [28,29] Our general ap-proach to obtain ternary M/Sn/E clusters is the expansion of organo-functionalized RSn/E clusters by addition of A 2 E( A = Na, SiMe 3 )a nd at ransition-metal salt to form the target compounds, [30][31][32][33][34][35][36] as trategy,w hich was first showcased by Merzweilera nd co-workers. [37] Several Sn/Cu/S clusters werer eported by other groups [37][38][39][40][41][42] as wella sb yo urselves, [30][31][32]43] yet only two discreteS n/Cu/Se compounds have been known so far.…”

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

“…two O atoms at two different Sn 2 S 2 rings are situated at one side of the Sn 4 plane, and the two others on the other side) to a crosswisetype orientation in D-with a distinguishable distortion of the [Sn 4 S 6 ] skeleton ( Figure 1). [5] In compound D, the average distance between the hydrazonic nitrogen atoms (C= N···N=C 630 pm) of each pair of arms provides enough space to introduce two NH 2 groups of hydrazine. We therefore assumed that for a reaction with D, ortho-phthalaldehyde might possess a suitable spacer length (670 pm) for bridging the proximal reactive sites without substantial changes of the original topology.…”

Organotin Selenide Clusters and Hybrid Capsules

“…The structures of the cations in 3-5 also conform to the explanation for the ligand arrangement and structuralr earrangement of the cluster core in terms of spacerl engths (C=N···N= C). [12] While the spacerl ength in 3 (4.33 )l ies within the range for an anti-parallel arrangemento ft he ligands (4)(5)(6), the spacer lengths in 4a, 4b,a nd 5 (9.44, 9.71, and 8.52 ,r espectively) are well above the lower limit for bigger capsules or cavitands (8 ). As indicated above,n oc avitand molecules were obtained yet, supposedly because we started directly from the defect-heterocubane unit instead of the "doubledecker"unit.…”

“…Although organotin selenide clusters with inert ligandsw ere synthesized and fully characterized as early as 1981, [2] the first exampleso fo rganotin selenide clusters with functional ligands have only been reportedr ecently, [3][4][5][6] which represent heavy homologues of known organotin sulfide clusters in most cases. [3,7,8] With theses tudies,w ew ere able to demonstrate that the reaction conditions, which eventually allow for the isolation of the seleniumc ompounds,r equire significant adaption and that both physical and chemical properties of the heavier homologues are notably different from the sulfide analogues.…”

“…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.…”