Synthesis, Crystal Structures and Properties of M3B3S6(M = Na, K, Rb) And LiSrB3S6

Püttmann, C.; Diercks, H.; Krebs, Bernt

doi:10.1080/10426509208055305

Cited by 41 publications

(13 citation statements)

References 5 publications

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“…Isolated monomeric cluster entities are known from the earlier published alkali metal selenoborato-closo-dodecaborates M 8 [39] without any lower substitution side products, only monosubstitution by a selenocyanate ligand is observed for a B 12 cluster even under basic conditions [40]. Another example of selenium bonding to a B 12 icosahedron is the binary boron selenide B 12 Se 2Ϫx B x [41]. Since it crystallizes in the B 6 P-type structure no close structural resemblance to the herein described selenoborates is present.…”

Section: Resultsmentioning

confidence: 99%

Na₂[B₁₈Se₁₆]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Hammerschmidt¹,

Döch²,

Pütz³

et al. 2005

Zeitschrift anorg allge chemie

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Systematic studies on selenoborates containing a B12 cluster entity and alkali metal cations led to the new crystalline phase Na2[B18Se16] which consists of a icosahedral B12 cluster completely saturated with trigonal‐planar BSe3 units and sodium counter‐ions. The cluster entities are connected to each other via seleno‐ and perselenobridges. Thus a three‐dimensional network results with [(B18Se12Se6/2)n]2−‐ and [(B18Se15Se6/2)n]2− anions in a ratio of 2:1. The new chalcogenoborate was prepared in a solid state reaction from sodium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 850 °C. Na2[B18Se16] crystallizes in the trigonal space group ${\rm P}{\bar 3}$ (no. 147) with a = 17.021(1) Å, c = 8.903(1) Å and Z = 3.

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Section: Resultsmentioning

confidence: 99%

Na₂[B₁₈Se₁₆]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Hammerschmidt¹,

Döch²,

Pütz³

et al. 2005

Zeitschrift anorg allge chemie

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“…Examples of completely substituted closo-dodecaboranes apart from halogenide or hydroxide substitued B 12 clusters [33±37] are rare. Although a hydrogen-selenium exchange succeeded in the formation of the cluster anion [B 6 (SeCN) 6 ] 2± [38] without any lower substitution side products, only monosubstitution by a selenocyanate ligand is observed for a B 12 cluster even under basic conditions [39]. Another example of selenium bonding to a B 12 icosahedron is the binary boron selenide B 12 Se 2±x B x [40].…”

Section: Resultsmentioning

confidence: 99%

Na6[B18Se17]: The First Selenoborato-closo-dodecaborate with a Polymeric Chain Anion

Hammerschmidt

Lindemann

Köster

et al. 2001

Z. anorg. allg. Chem.

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Systematic studies on selenoborates containing a B 12 cluster entity and alkali metal cations led to the new crystalline phase Na 6 [B 18 Se 17 ] which consists of a icosahedral B 12 cluster completely saturated with trigonal-planar BSe 3 units and sodium counter-ions. Neighbouring cluster entities are connected in one direction via exocyclic selenium atoms forming the infinite chain anion ([B 18 Se 16 Se 2/2 ] 6± ) ¥ . The new chalcogenoborate was prepared in a solid state reaction from sodium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 850°C. Na 6 [B 18 Se 17 ] crystallizes in the monoclinic space group C2/c (no. 15) with a = 18.005(4) A Ê , b = 16.549(3) A Ê , c = 11.245(2) A Ê , b = 91.35(3)°and Z = 4. Na 6 [B 18 Se 17 ]: Das erste Selenoborato-closo-dodecaborat mit polymerer Kettenstruktur Inhaltsu È bersicht. Gezielte Versuche zur Synthese neuer Selenoborato-closo-dodecaborate fu È hrten im terna È ren Phasengebiet Na/B/Se zu der neuen Verbindung Na 6 [B 18 Se 17 ], in der ein vollsta È ndig durch Chalkogen abgesa È ttigter B 12 -Ikosaeder vorliegt. Benachbarte Clustereinheiten sind durch exocyclische Selenatome gegenu È berliegender BSe 3 -Liganden zu eindimensional unendlichen Ketten verknu È pft. Das neue Chalkogenoborat wurde in einer Hochtemperatur-Feststoffreaktion aus Natriumselenid, amorphem Bor und Selen in graphitierten, evakuierten Quarzglasampullen hergestellt. Na 6 [B 18 Se 17 ] kristallisiert in der monoklinen Raumgruppe C2/c (Nr. 15) mit den Gitterparametern a = 18,005(4) A Ê , b = 16,549(3) A Ê , c = 11,245(2) A Ê , b = 91,35(3)°und Z = 4.

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“…Compounds with boron–chalcogen bonds comprise the chalcoborate class, which features a variety of structural motifs typically with B 3+ in either a trigonal or tetrahedral coordination. For example, binary boron sulfides crystallize in structures containing molecular to polymeric units such as porphyrin-like B 8 S 16 or polymeric (BS 2 ) n , whereas ternary and quaternary boron chalcogenides feature anionic species with trigonal B atoms such as (B(S/Se) 3 ) 3– , (B 2 S 5 ) 2– , and (B 3 S 6 ) 3– , and even corner-sharing BS 4 tetrahedra, as observed in the framework compounds Li 9 B 19 S 33 and Li 4–2 x Sr 2+ x B 10 S 19 ( x = 0.27) . A common characteristic of these chalcoborate phases is that they are very moisture sensitive and difficult to handle.…”

Section: Introductionmentioning

confidence: 99%

Sn_4−δB₁₂Se₁₂[Q_x], Q = Se, Te, a B₁₂ Cluster Tunnel Framework Hosting Neutral Chalcogen Chains

et al. 2021

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We report the open framework semiconductor, Sn 4 B 12 Se 12 , synthesized using a Sn/Se flux method. The framework in this compound features the rare icosahedral [B 12 Se 12 ] 14− anion assembled into a 3D tunnel structure with open tunnels and is chemically stable over a wide pH range from concentrated nitric acid to 3 M NaOH aqueous solution. The rigid nature of this structure and high chemical stability allows chemical strategies for the removal of Se chains from the tunnels, giving an empty tunnel structure and subsequent insertion of tellurium chains as confirmed through single-crystal X-ray diffraction. The assynthesized Sn 4 B 12 Se 12 [Se 3.80 ] contains selenium chains in the tunnels and crystallizes in the hexagonal space group P6 3 22 with a = b = 13.5927(7) Å, c = 9.8167(5) Å. After removal of Se and subsequent Te insertion, the space group remains the same with small changes in lattice parameters and occupancy of tin sites. The experimentally obtained optical band gap of the as-synthesized material is 1.66 eV and can be modulated by chemical modifications. DFT calculations of the empty framework show an indirect nature of the band gap calculated at 1.16 eV. The neutral framework of Sn 4 B 12 Se 12 is a new example of a microporous semiconductor with exceptional stability and electronic properties that stem from the presence of icosahedral boron clusters.

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Synthesis, Crystal Structures and Properties of M₃B₃S₆(M = Na, K, Rb) And LiSrB₃S₆

Cited by 41 publications

References 5 publications

Na₂[B₁₈Se₁₆]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Na₂[B₁₈Se₁₆]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Na6[B18Se17]: The First Selenoborato-closo-dodecaborate with a Polymeric Chain Anion

Sn_4−δB₁₂Se₁₂[Q_x], Q = Se, Te, a B₁₂ Cluster Tunnel Framework Hosting Neutral Chalcogen Chains

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Synthesis, Crystal Structures and Properties of M3B3S6(M = Na, K, Rb) And LiSrB3S6

Cited by 41 publications

References 5 publications

Na2[B18Se16]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Na2[B18Se16]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Na6[B18Se17]: The First Selenoborato-closo-dodecaborate with a Polymeric Chain Anion

Sn4−δB12Se12[Qx], Q = Se, Te, a B12 Cluster Tunnel Framework Hosting Neutral Chalcogen Chains

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Synthesis, Crystal Structures and Properties of M₃B₃S₆(M = Na, K, Rb) And LiSrB₃S₆

Na₂[B₁₈Se₁₆]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Na₂[B₁₈Se₁₆]: The First 3D Polymeric Selenoborato‐closo‐dodecaborate

Sn_4−δB₁₂Se₁₂[Q_x], Q = Se, Te, a B₁₂ Cluster Tunnel Framework Hosting Neutral Chalcogen Chains