Bi 2 O(XO 4 )(IO 3 ) 2 (X = S, Se, Cr): Three-dimensional frameworks containing [Bi 4 O 2 ] 8+ clusters

Synthesis, Crystal Structures, Spectroscopic Characterization, and Thermal Analyses of the New Bismuth Sulfates NaBi(SO4)2·H2O and ABi(SO4)2 (A = K, Rb, Cs)

“…[46] The bands of the sulfate groups, in particular their asymmetric S-O stretching vibrations, of the four compounds 1-4 can be observed at 1112 and 1186 cm -1 for 1, 1292 and 1112 cm -1 for 2, and 1112 cm -1 for 3-4, which are, e.g., reported for Bi 2 O(SO 4 ) (IO 3 ) 2 and BiCu 2 (TeO 3 )(SO 4 )(OH) 3 with bands at 1130 and 1069 cm -1 , 1110, 1092, and 1071 cm -1 , respectively. [29,31] The S-O asymmetric bending vibrations are found at 646, 621, and 586 cm -1 for 1, 617, 582 cm -1 for 2, 642, 617, and 592 cm -1 for 3, 642, 617, and 587 cm -1 for 4, in agreement with the Na 6 M(SO 4 ) 4 •2H 2 O (M = Co, Ni) with bands at 619 and 620 cm -1 . [47] The bands at 893 and 942 cm -1 in the infrared spectrum of 2 are assigned to the S-O symmetric stretching vibration.…”

“…[47] The bands at 893 and 942 cm -1 in the infrared spectrum of 2 are assigned to the S-O symmetric stretching vibration. Such vibration is also reported in the IR spectra of Bi 2 O(SO 4 )(IO 3 ) 2 [29] at 856 and 885 cm -1 and BiCu 2 (TeO 3 ) (SO 4 )(OH) 3 [31] at 976 cm -1 . Observed absorption bands at 465 cm -1 for 1 and 2, 465, 437 cm -1 for 3, and 437 cm -1 for 4 are assigned to vibrations of the Bi-O bonds, respectively.…”

“…Observed absorption bands at 465 cm -1 for 1 and 2, 465, 437 cm -1 for 3, and 437 cm -1 for 4 are assigned to vibrations of the Bi-O bonds, respectively. These vibrations are also observed in the IR spectra of Bi 2-O(SO 4 )(IO 3 ) 2 [29] at 420, 443, 508 and 521 cm -1 , BiCu 2 (TeO 3 ) (SO 4 )(OH) 3 [31] at 468 and 461 cm -1 , and Bi 2 TeO 5 [48] at 465 cm -1 .…”

ABi2(IO3)2F5 (A=K, Rb, and Cs): A Combination of Halide and Oxide Anionic Units To Create a Large Second‐Harmonic Generation Response with a Wide Bandgap

“…and the BiÀFb ond length ranging from 2.220(24) to 2.425(22) .A nother Bi atom is five-coordinated by Fa toms to form [BiF 5 ] 2À anionic group with the Bi À Fb ond length in the range of 2.059(21)-2.323(21) .E very Ia tom is bonded to three Oa toms to build [IO 3 ] À anionic groups with the IÀObond length ranging from 1.788(28) to 1.877(28) .A ll the covalent bonds including Bi À F, Bi À O, and I À Ob onds in [BiO 2 F 4 ] 5À , [BiF 5 ] 2À ,a nd [IO 3 ] À anionic groups are not identical, which leads to the large structural distortion with asymmetric and polar characteristics owing to the lone-pair electrons of Bi 3+ and I 5+ cations.E ach [BiO 2 F 4 ] 5À unit is connected to four [BiF 5 ] 2À groups by different Fa toms to form at wo-dimensional (2D) layered [Bi 2 (IO 3 ) 2 F 5 ] À anionic framework in which two [IO 3 ] À groups are linked to [BiO 2 F 4 ] 5À unit through two bridged Oa toms on the same side;o ne Fa tom in the [BiF 5 ] 2À group does not take part in the bridged connection to locate on the other side (…”

“…As they belong to ai somorphic crystal system with the same structure,o nly KBi 2 (IO 3 ) 2 F 5 (1)i ss hown so as to illustrate the novel structure of ABi 2 (IO 3 ) 2 F 5 (A = K, Rb,a nd Cs) crystals in detail. Theasymmetric unit cell of 1 contains one Katom, two Bi atoms,two Iatoms,six Oatoms,and five Fatoms.One Bi atom is linked to two Oa toms and four Fa toms to form [BiO 2 F 4 ] 5À anionic group with the BiÀObond length ranging from 2.372(24) to 2.385 (22) and the BiÀFb ond length ranging from 2.220(24) to 2.425 (22) .A nother Bi atom is five-coordinated by Fa toms to form [BiF 5 ] 2À anionic group with the Bi À Fb ond length in the range of 2.059(21)-2.323(21) .E very Ia tom is bonded to three Oa toms to build [IO 3 ] À anionic groups with the IÀObond length ranging from 1.788(28) to 1.877(28) .A ll the covalent bonds including Bi À F, Bi À O, and I À Ob onds in [BiO 2 F 4 ] 5À , [BiF 5 ] 2À ,a nd [IO 3 ] À anionic groups are not identical, which leads to the large structural distortion with asymmetric and polar characteristics owing to the lone-pair electrons of Bi 3+ and I 5+ cations.E ach [BiO 2 F 4 ] 5À unit is connected to four [BiF 5 ] 2À groups by different Fa toms to form at wo-dimensional (2D) layered [Bi 2 (IO 3 ) 2 F 5 ] À anionic framework in which two [IO 3 ] À groups are linked to [BiO 2 F 4 ] 5À unit through two bridged Oa toms on the same side;o ne Fa tom in the [BiF 5 ] 2À group does not take part in the bridged connection to locate on the other side ( Figure 1a). More interestingly,t wo adjacent 2D layered [Bi 2 (IO 3 ) 2 F 5 ] À anionic frameworks are arranged in opposite directions to construct adouble-layered structure.All the [IO 3 À ]units in each separated [Bi 2 (IO 3 ) 2 F 5 ] À network are almost aligned in the same way,a nd the alkali metal ions are inserted into the double-layered space to bond with the hanging Fatom of BiÀFbonds via ionic interaction to construct af inal 3D structural topology of 1 (Figure 1b; Supporting Information, Figure S5).…”