The investigation of the coordination chemistry of rare-earth metal complexes with cyanide ligands led to the isolation and crystallographic characterization of the Ln III cyanotriphenylborate complexes dichlorido(cyanotriphenylborato-κ N )tetrakis(tetrahydrofuran-κ O )lanthanide(III), [ Ln Cl 2 (C 19 H 15 BN)(C 4 H 8 O) 4 ] [lanthanide ( Ln ) = dysprosium (Dy) and yttrium Y)] from reactions of LnCl 3 , KCN, and NaBPh 4 . Attempts to independently synthesize the tetraethylammonium salt of (NCBPh 3 ) − from BPh 3 and [NEt 4 ][CN] in THF yielded crystals of the phenyl-substituted cyclic borate, tetraethylazanium 2,2,4,6-tetraphenyl-1,3,5,2λ 4 ,4,6-trioxatriborinan-2-ide, C 8 H 20 N + ·C 24 H 20 B 3 O 3 − or [NEt 4 ][B 3 (μ-O) 3 (C 6 H 5 ) 4 ]. The mechanochemical reaction of BPh 3 and [NEt 4 ][CN] without solvent produced crystals of tetraethylazanium cyanodiphenyl-λ 4 -boranyl diphenylborinate, C 8 H 20 N + ·C 25 H 20 B 2 NO − or [NEt 4 ][NCBPh 2 (μ-O)BPh 2 ]. Reaction of BPh 3 and KCN in THF in the presence of 2.2.2-cryptand (crypt) led to a crystal of bis[(2.2.2-cryptand)potassium] 2,2,4,6-tetraphenyl-1,3,5,2λ 4 ,4,6-trioxatriborinan-2-ide cyanomethyldiphenylborate tetrahydrofuran disolvate, 2C 18 H 36 KN 2 O 6 + ·C 24 H 20 B 3 O 3 − ·C 14 H 13 BN − ·2C 4 H 8 O or [K(crypt)] 2 [B 3 (μ-O) 3 (C 6 H 5 ) 4 ][NCBPh 2 Me]·2THF. The [NCBPh 2 (μ-O)BPh 2 ] 1− and (NCBPh 2 Me) 1− anions have not been structurally characterized previously. The structure of 1-Y was refined as a two-component twin with occupancy factors 0.513 (1) and 0.487 (1). In 4 , one solvent molecule was disordered and included using multiple components with partial site-occupancy factors. 
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                            Correlating magnetic anisotropy with [Mo(CN) 7 ] 4− geometry of Mn II –Mo III magnetic frameworks
                        
                    
    
            Four new three-dimensional (3-D) coordination frameworks based on the heptacyanomolybdate( iii ) anion were prepared and characterised by magnetic measurements: {[Mn II (imH) 2 ] 2 [Mn II (H 2 O)(imH) 3 ][Mn II (imH) 4 ] [Mo III (CN) 7 ] 2 ·6H 2 O} n ( 1 ) (imH = imidazole), {[Mn II (H 2 O) 2 (imH)] 3 [Mn II (H 2 O)(imH) 2 ][Mo III (CN) 7 ] 2 ·5H 2 O} n ( 2 ), {[Mn II (Htrz)(H 2 O) 2 ][Mn II (Htrz) 0.7 (H 2 O) 2.3 ][Mo III (CN) 7 ]·5.6H 2 O} n ( 3 ) (Htrz = 1,2,4-triazole) and {[Mn II (H 2 O) 2 ] 3 [Mn II (H 2 O) 4 ][Mo III (CN) 7 ] 2 ·6H 2 O·2urea} n ( 4 ). All four compounds exhibit long-range ferrimagnetic ordering and exhibit an opening of their magnetic hysteresis loops at 1.8 K; 1 and 2 exhibit the highest coercive fields among all known [Mo III (CN) 7 ]-based assemblies, 5000 and 4500 Oe respectively. The coercivity of 1–4 is correlated with the geometry of the heptacyanomolybdate( iii ) anion and the cyanide bridging pattern. A paramagnetic analogue of compound 1 , {[Mn II (imH) 2 ] 2 [Mn II (H 2 O)(imH) 3 ][Mn II (imH) 4 ][Re III (CN) 7 ] 2 ·6H 2 O} n ( 1Re ), where the heptacyanomolybdate( iii ) anion is substituted by the diamagnetic heptacyanorhenate( iii ) anion is also reported which constitutes the first example of a coordination framework based on [Re III (CN) 7 ] 4− . 
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                            - Award ID(s):
- 1808779
- PAR ID:
- 10108460
- Date Published:
- Journal Name:
- Dalton Transactions
- ISSN:
- 1477-9226
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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