Simple Quaternary Ammonium Ions R4N+ (R=nPr, nBu, nPen) as Versatile Structure Directors for the Synthesis of Zeolite-Like, Heterobimetallic Cyanide Frameworks

Metathesis Reactions of the super-Prussian Blue Systems [(Me3Sn)3M(CN)6] (M=Co, Ir) with, inter alia, Tetrapropylammonium (and -phosphonium) Ions: Crystal Structures of [(nPr4P)(Me3Sn)2Co(CN)6·2H2O] and [(nPr4N)(Me3Sn)2Ir(CN)6·2H2O]

“…The X-ray powder di!ractogram (XRD) of 3 resembles strongly the XRDs of 1 and 2, manifesting that again in"nite [ } Ir}CN}Sn}NC } ] chains constitute a corresponding 3-D framework for 3 as known for 1 (6, 11). However, in surprising contrast to our earlier "ndings (7,8), according to which suspensions of 1 and 2 in solutions containing the ion Me N> or Et N> remain completely unchanged, 3 is found to redissolve completely in solutions of the salts Me NI or Et NCl. On the other hand, a suspension of 3 in aqueous solutions of nPr NCl and nPr PBr, respectively, a!ords in acceptable yields (i.e., of ca.…”

“…The chemical compositions of 1a-P, 3a, 3a-P, 3b, and 3c could be established by combining independent results from elemental analysis and H NMR spectroscopy in D O/NaOD solution. The latter, quite elegant technique allows the independent determination of the respective R E/Me Sn ratios (7,8). According to its elemental analysis, 3c seems to be richer in H O (m52) than 1c and 2c (8).…”

“…Coordinative H OPSn and CNPSn interactions as well as OH 2NC and eventually even weak CH 2NC hydrogen bonds appear to be responsible for the generation of the various structural designs. Most interestingly, only the nPr N> ion was found to completely abandon the otherwise preferred motif of in"nite or "nite [M}CN}Sn}NC] L chains (8). To examine how signi"cantly a subtle tuning of the basic building blocks R E>, [M(CN) 6 ]\, and Me Sn>, respectively, may a!ect the concerted structure-directing in#uence of the various comparatively weak modes of interaction, the present study is extended particularly toward the related building blocks nPr P> and [Ir(CN) 6 ]\, respectively.…”

“…It is important to point out that the notation adopted here is not identical to that used in our previous contributions (7,8 …”

“…While, however, structural details about as-prepared (i.e., noncalcined) zeolites are still scarce (4), there is increasing evidence that polymeric metal cyanides may serve as suitable R E> acceptors. For instance, the reaction of Hg(CN) 2 with MCN (M"Li, Na, K) and R NCN in H O a!ords precipitates of di!erent Hg/M/R N ratios, depending essentially on the size of the alkyl group R (5 [1] a!ording with R"n-propyl (nPr), n-butyl (nBu), and n-pentyl (nPen), respectively, again sparingly water-soluble, although water-containing products of surprisingly versatile structures (7,8). Coordinative H OPSn and CNPSn interactions as well as OH 2NC and eventually even weak CH 2NC hydrogen bonds appear to be responsible for the generation of the various structural designs.…”