Salts with the Triborate Anion [B₃O₃F₂(OH)₂]^–: A Combined Experimental and Theoretical Study

Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals

“…The 11 B{ 19 F}‐REDOR spectrum was carried out to establish the existence of B−F bonds, the results clearly proved that there is tetrahedrally coordinated B with B−F bonds in NBF. In addition, these results were similar to the data of [Ph 4 P][B 3 O 3 F 2 (OH) 2 ] ( δ =140.1 in its 19 F MAS NMR spectrum, which also contains the same [B 3 O 3 F 2 (OH) 2 ] units with our compound) [14] . The OH groups in NBF exhibit three different coordination environments, thus the 1 H MAS NMR spectrum shows three distinguishable resonances at δ =7.5, 6.9, and 2.4 ppm (Figure 2 a), which fits very well the solved single crystal results.…”

“…The bond valence sum (Table S2 in the SI), observation of strong hydrogen interactions, and conventional structural configuration of OH/F in three‐ and four‐coordinated B−O units (Table S4 in the SI), give preliminary confirmation of well‐ordered OH/F anions in NBF crystal. The final solved structure is in agreement with those reported organic borates with the same [B 3 O 3 F 2 (OH) 2 ] units in [Ph 4 P][B 3 O 3 F 2 (OH) 2 ] and [Ph 3 MeP][B 3 O 3 F 2 (OH) 2 ] as well as [B(OH) 3 ] in Ca 2 [B 5 O 8 (OH)] 2 [B(OH) 3 ]⋅H 2 O and Ba 3 (OH)(B 9 O 16 )B(OH) 3 , etc., [14, 15] which is the strong structural evidence for that.…”

“…Thebond valence sum (Table S2 in the SI), observation of strong hydrogen interactions,a nd conventional structural configuration of OH/F in three-and four-coordinated BÀO units (Table S4 [14,15] which is the strong structural evidence for that.…”

Computational 19F NMR. 1. General features

“…Some early computational work (aimed at benchmarking and validation) included F 2 as test molecule, which proved to be challenging [26][27][28]. Interest in modeling 19 F shifts has steadily continued, and several papers have appeared in the last decade aimed at general structural issues, solution chemistry and physical organic chemistry, [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] solid-state issues (especially the prediction of chemical shift tensors), [47][48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] J-couplings [65][66][67][68][69][70][71][72]…”

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)

“…[14] Double deprotonation of this anion resulted in a carbon extrusion/cluster contraction reaction yielding the cyano-closo-undecaborate dianion [3-NC-closo-B 11 F 10 ] 2À , [42] which takes part in further unprecedented reactions. [42,43] These unexpected findings tempted us to investigate the chemistry of other, especially fluorinated, aminocarba-closododecaborate anions. Since the starting materials for these studies-the non-fluorinated amines-are unknown or they are only available in trace amounts, their preparation was attempted.…”