New organically templated vanadium tellurites: (H₂pn)[V₂TeO₈] (pn is propane-1,3-diamine)

Abstract

The title compound, poly[propane-1,3-diaminium hexa-mu-oxido-dioxidotellurium(IV)divanadium(V)], (C3H12N2)[V2O8Te] or (H2pn)[V2TeO8] (pn is propane-1,3-diamine), contains a two-dimensional anionic layer and the diprotonated pn cation for charge compensation. The anionic layer consists of pyrovanadates and [TeO3] pyramids, which are linked alternately through corner-sharing to form a one-dimensional chain. These one-dimensional chains are crosslinked through two weak Te-O bonds, constructing an anionic layer. Hydrogen bonds are observed involving the diprotonated pn cation and the O atoms of the anionic framework.

Role of Hydrogen-Bonding in the Formation of Polar Achiral and Nonpolar Chiral Vanadium Selenite Frameworks

“…Templated vanadium tellurites and selenites represent attractive systems for study, owing to the presence of multiple asymmetric building units, including the possibility of chiral organic amines, out-of-center octahedral distortions on vanadium cations, and stereoactive lone pairs on the Te 4+ and Se 4+ centers. Within the small number of reported templated vanadium tellurites, − both framework and noncentrosymmetric compounds are observed . However, neither noncentrosymmetric nor framework structures have been reported in templated vanadium selenites. − Yet, templated vanadium selenites represent particularly interesting because the much higher water solubility of SeO 2 versus TeO 2 suggests the promise of wider structural and compositional flexibility with respect to templated tellurites.…”

“…Within the small number of reported templated vanadium tellurites, − both framework and noncentrosymmetric compounds are observed . However, neither noncentrosymmetric nor framework structures have been reported in templated vanadium selenites. − Yet, templated vanadium selenites represent particularly interesting because the much higher water solubility of SeO 2 versus TeO 2 suggests the promise of wider structural and compositional flexibility with respect to templated tellurites.…”

The Role of Stereoactive Lone Pairs in Templated Vanadium Tellurite Charge Density Matching

“…This study was designed to better elucidate formation mechanisms by isolating the effects of amine structure. Compound 1, [C 3 H 12 N 2 ][V 2 TeO 8 ], 22 and [C 4 H 12 N 2 ][(VO 2 )-(TeO 3 )] 2 21 were all synthesized under nearly identical reaction conditions using NaVTeO 5 as a source of both V 5þ and Te 4þ . These three compounds were synthesized from reaction gels with fixed 1 NaVTeO 5 :8 amine ratio in a 1:1 ethanol/ H 2 O solution.…”

“…[5][6][7][8][9][10] Materials that possess crystallographic non-centrosymmetry are of great interest to researchers because they can exhibit several desirable physical properties, 11 including nonlinear optical activity, such as second harmonic generation (SHG) and piezoelectricity. 12,13 Despite the breadth of templated metal selenite chemistry and interest in metal tellurites that do not contain organic templates, [14][15][16][17][18][19] only six organically templated metal tellurites have been reported: [C 2 H 10 N 2 ][VTe 3 O 9 ], 20 [C 2 H 10 N 2 ][V 2 Te 2 O 10 ] 3 H 2 O, 21 [C 4 H 12 N 2 ][(VO 2 )(TeO) 3 ] 2 , 21 [C 3 H 12 N 2 ][V 2 TeO 8 ], 22 23 and [C 2 H 10 N 2 ][VTeO 5 ] 2 . 24 A number of reaction mechanisms have been postulated for the formation of organically templated inorganic materials.…”

“…First, low coordination numbers on cationic centers promote directional covalent bonding, which in turn is beneficial in the creation of new microporous materials . Second, local acentricity on framework building units is a well-established route to crystallographic non-centrosymmetry. − Materials that possess crystallographic non-centrosymmetry are of great interest to researchers because they can exhibit several desirable physical properties, including nonlinear optical activity, such as second harmonic generation (SHG) and piezoelectricity. , Despite the breadth of templated metal selenite chemistry and interest in metal tellurites that do not contain organic templates, − only six organically templated metal tellurites have been reported: [C 2 H 10 N 2 ][VTe 3 O 9 ], [C 2 H 10 N 2 ][V 2 Te 2 O 10 ]·H 2 O, [C 4 H 12 N 2 ][(VO 2 )(TeO) 3 ] 2 , [C 3 H 12 N 2 ][V 2 TeO 8 ], [C 4 H 15 N 3 ][V 2 Te 2 O 10 ]·2H 2 O, and [C 2 H 10 N 2 ][VTeO 5 ] 2 …”