Transformation of [EMIm][BPB] into a Cationic Luminescent Ln‐Coordination Polymer with the Bis(phthalato)borate Anion

Abstract

Starting from phthalic acid and Na[BH4], the low‐melting salt [EMIm+][BPB] [EMIm+ = 1‐ethyl‐3‐methylimidazolium; BPB– = bis(phthalato)borate] was synthesized and further reacted with Tb(NO3)3·6H2O to yield the one‐dimensional coordination polymer 1∞[Tb(o‐HBDC)(H2O)6][BPB]2. Product formation is a result of the formation of the ortho‐phthalato mono acid (o‐HBDC) from [BPB]– anions in the process and leads to linkage of adjacent Tb3+ ions resulting in the cationic strand 1∞[Tb(o‐HBDC)]2+. The cationic charge of the coordination polymer is compensated by the [BPB]– anions in the crystal structure. Furthermore, the one‐dimensional coordination polymer 1∞[Tb(o‐HBDC)(H2O)6][BPB]2 shows characteristic luminescence based on the 4f–4f transitions of the Tb3+ ions upon excitation with UV light.

Syntheses, structures, photoelectric properties and photocatalysis of iodobismuthate hybrids with lanthanide complex cations

“…The Ln–O bond lengths are in the range of 2.344(7)–2.448(7) Å for Eu–O (Table S3†) and 2.331(16)–2.456(13) Å for Tb–O (Table S4†). They are in the range of those observed in the Eu( iii ) and Tb( iii ) complexes with EuO 8 and TbO 8 coordination polyhedra, 15,16 respectively. In 3 , the disordered atoms I4 and I5 were refined as 92% and 8% occupancies, and the disordered atom Bi4 was refined as 90% and 10% occupancies.…”

“…The Ln-O bond lengths are in the range of 2.344(7)-2.448( 7) Å for Eu-O (Table S3 †) and 2.331( 16)-2.456(13) Å for Tb-O (Table S4 †). They are in the range of those observed in the Eu(III) and Tb(III) complexes with EuO 8 and TbO 8 coordination polyhedra, 15,16…”

Statistic Replacement of Lanthanide Ions in Bis‐salicylatoborate Coordination Polymers for the Deliberate Control of the Luminescence Chromaticity

“…A few examples of Ln‐compounds are known of the anions tetra(methoxy)borate or catecholatoborate, namely [Ln{B(OCH 3 ) 4 }(NO 3 ) 2 (CH 3 OH) 2 ] (Ln=La, Pr, Nd) [11] and [{Na}{(sal) 3 Ln(B(OCH 3 ) 4 )Ln(sal) 3 }] n (sal=salicylato and Ln=Y, Nd, Eu−Lu) [12] and [(η 2 ‐catecholato‐μ‐catecholatoborate) 3 Ln(thf) 3 ]⋅thf (Ln=Nd, Sm) [13] . In this context, we could also show that the low‐melting salt [EMIm][BPB] ([BPB] − =bis(phthalato)borate anion; [B{(C 6 H 4 )(CO 2 CO 2 )} 2 ] − ) could be transformed into a coordination polymer together with Tb 3+ , 1 ∞ [Tb(o‐HBDC)(H 2 O) 6 ][BPB] 2 [14] …”

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

“…zeolites) [12–24] . Besides application in classic solid state chemistry, ILs can be used as reaction media to prepare (oligomeric) metal complexes, metal organic frameworks, coordination polymers [25–35] or cluster compounds incorporating main group elements [36–41] . Within SPP 1708, the synthesis of intermetallic cluster and nanoparticles, [3,42–56] the controlled synthesis of polyanions and cations, [57–61] solvent‐free chalcogenidometal‐containing materials, [62–75] deposition of nanocrystalline materials, [76–80] ionic liquids as precursors for inorganic materials, [81–83] ionic‐liquid‐modified hybrid materials, [84–87] as well as the low‐temperature synthesis of thermoelectric materials [88–92] were investigated.…”

“…[5] Even after six years of SPP 1708, utilization of ILs as reaction media for the synthesis of inorganic compounds is still a fairly new area steadily growing and with the focus on metal/metal oxide/metal nitride/metal halide (nano)particles of different types, [6][7][8][9][10] semiconductors, [11] and inorganic solids (e. g. zeolites). [12][13][14][15][16][17][18][19][20][21][22][23][24] Besides application in classic solid state chemistry, ILs can be used as reaction media to prepare (oligomeric) metal complexes, metal organic frameworks, coordination polymers [25][26][27][28][29][30][31][32][33][34][35] or cluster compounds incorporating main group elements. [36][37][38][39][40][41] Within SPP 1708, the synthesis of intermetallic cluster and nanoparticles, [3,[42][43][44][45][46][47][48]…”