Syntheses and crystal structures of several novel alkylammonium iodobismuthate materials containing the 1,3-bis-(4-piperidinium)propane cation

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Abstract

The inorganic–organic salts (H2TMDP)3(Bi2I9)2 (1), (H2TMDP)2(Bi4I16)·2EtOH (2), (H2TMDP)2(Bi6I22)·2EtOH (3), and (H2TMDP)2(Bi6I22) (4) were synthesized and structurally characterized from the solvothermal reaction of 1,3-bis-(4-piperidyl)propane (TMDP) and BiI3 by adjusting the relative ratio of the reactants. The anions of the compounds consist of 2 (1), 4 (2), or 6 (3 and 4) BiI6 polyhedra, which are joined by face- (1) or edge-sharing (24) to form discrete anions. The size of the discrete anion, in terms of the number of connected polyhedra, is observed to increase as the ratio of BiI3 to TMDP is increased. A related compound (H2TMDP)(Bi3I11)·(H2O) (5) was synthesized and structurally characterized using the same two reactants in the presence of HF. The anion of 5 is polymeric rather than discrete, with a trioctahedral repeat unit.

Graphical abstract

The syntheses and single-crystal X-ray structures of five new inorganic–organic compounds containing the alkylammonium cation 1,3-bis-(4-piperidinium)propane in addition to a complex iodobismuthate anion are presented and discussed. In general, structures having larger anions are produced from greater relative ratios of the inorganic starting material to the organic starting material.

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Introduction

The chemistry of the main group metal halides has been widely explored for several decades owing to the interesting physical properties that have often been observed in such systems including luminescence, semiconductivity, and second-order non-linear optical activity [1], [2], [3], [4], [5]. To date, numerous metal–halide systems involving Sn, Pb, Sb, Bi, and Te have been synthesized and structurally characterized [1], [2], [3], [4], [5], [6], [7], [8], [9], [10]. In general, these systems contain a complex metal–halide anion in which MXn (M=metal, X=halide) coordination polyhedra are linked by corner-, edge-, or face-sharing. Charge balance in these systems is typically provided by an organic cation, although it has been demonstrated that inorganic cations or metal coordination cations are also viable charge-balancing counter-ions [11], [12], [13], [14].

In addition to the promising physical properties observed in this family of materials, tremendous structural diversity is also encountered—particularly with respect to the dimensionality, size, and connectivity of the anionic component. The anionic metal–halide species has been observed to range in dimensionality from two-dimensional (2-D) or one-dimensional (1-D) polymeric anions to discrete anions of various sizes. The size and dimensionality of the anionic component is tied to the specific reaction conditions employed, particularly the identity of the metal and the size, charge density, and relative concentration of the cation. Because of the ability to influence the dimensionality and size of the anionic component, size- and dimensionality-dependent physical properties (i.e., quantum confinement effects) may be observed in such systems.

The bismuth(III) trihalides (BiX3) have been employed in the synthesis of numerous metal–halide materials owing to the ability of Bi3+ to function as a good Lewis acid and a strong halide ion acceptor [15], [16]. Typically, BiX3 is reacted in the presence of a cation source and a halide ion source to produce the halobismuthate compound, where formation of the anionic species is thought to occur via uptake of X by neutral BiX3. X anions may be supplied to Bi3+ either by the cationic reagent, by a haloacid (HX), or by BiX3 itself [9], [17], [18]. With respect to the cations, alkylamines, or alkylammonium halides have been employed as cationic reagents by us and others with great success [1], [10], [19], [20]. In cases where an alkylamine is employed as the cationic reagent, protonation of the alkylamine during the solvothermal synthesis is observed.

This paper describes the solvothermal syntheses and X-ray structural analyses of a series of alkylammonium iodobismuthate materials synthesized from BiI3 and the alkylamine 1,3-bis-(4-piperidyl)propane (TMDP). The size dependence of the anionic component on the relative concentration of reagents is examined along with the influence of additional reagents (i.e., HF) on the nature of the anion formed.

Section snippets

Materials

BiI3 (Alfa Aesar, 95%), trimethylenedipiperidine monohydrate (TMDP·H2O, also called 1,3-bis(4-piperidyl)propane monohydrate, Lancaster, 98%), ethanol (AAPER, 100%), and aqueous HF (Fisher, 49% solution) were purchased from commercial sources and used as received.

Synthesis of (H2TMDP)3(Bi2I9)2 (1)

BiI3 (50 mg, 0.08 mmol), TMDP·H2O (13 mg, 0.06 mmol), and 6 mL absolute ethanol were added to a 23 mL Teflon lined autoclave, and the contents were stirred for several minutes prior to sealing the vessel. The autoclave was heated to 140 °C at

Results and discussion

Single crystals of (H2TMDP)3(Bi2I9)2 (1), (H2TMDP)2(Bi4I16)·2EtOH (2), (H2TMDP)2(Bi6I22)·2EtOH (3), (H2TMDP)2(Bi6I22) (4), and (H2TMDP)(Bi3I11)·H2O (5) were all grown solvothermally using ethanol as the reaction solvent. The reaction producing each product involves the in situ formation of an anionic species from the neutral starting material BiI3. Charge balance for the anion is provided by TMDP, a conformationally flexible organic diamine, which becomes protonated under the specific reaction

Conclusion

Single crystals of five new inorganic–organic salts have been grown solvothermally from BiI3 and trimethylenedipiperidine hydrate (TMDP·H2O). In the absence of other reagents, it was determined that the size of the inorganic anion increases as the ratio BiI3:TMDP increases. While mixed halide anions of bismuth(III) have been observed upon introduction of a haloacid (HCl or HBr) to the TMDP/BiI3 system, a polymeric iodobismuthate anion is observed to be the product upon addition of HF. Thus, it

Supporting information

CCDC-271581-85 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033; E-mail: [email protected]].

Acknowledgments

Financial support of this project was provided by the National Science Foundation through grant numbers CHE:0314164 and CHE:0315152.

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