BaB2S4: An Efficient and Air-Stable Thioborate as Infrared Nonlinear Optical Material with High Laser Damage Threshold

Li5B7S13 (C2/c; a = 17,304(2) A, b = 21,922(3) A, c = 12,233(2) A, β = 134,91(1)°; Z = 8 und Li9B19S33 (C2/c; a = 23,669(9) A, b = 14,361(3) A, c = 12,237(3) A, β = 103,77(2)°; Z = 4 wurden durch Reaktion von stochiometrischen Mengen Lithiumsulfid, Bor und Schwefel bei 750°C (Li5B7S13) und 700°C (Li9B19S33) mit anschliesendem Tempern dargestellt. Die Kristallstrukturen bestehen aus sich durchdringenden, polymeren Bor-Schwefel-Anionengerusten, die durch Eckenverknupfung von B4S10- und B10S20-Einheiten (Li5B7S13) bzw. B19S36-Einheiten (Li9B19S33) gebildet werden. Dazwischen befinden sich die Lithiumkationen, wobei bei Li9B19S33 eine starke Fehlordnung beobachtet wird.



Li5B7S13 and Li9B19S33: Two Lithium Thioborates with Novel Highly Polymeric Anion Networks



Li5B7S13 (C2/c; a = 17.304(2) A, b = 21.922(3) A, c = 12.233(2) A, β = 134.91(1)°; Z = 8) and Li9B19S33 (C2/c; a = 23.669(9) A, b = 14.361(3) A, c = 12.237(3) A, β = 103.77(2)°; Z = 4) were prepared by reaction of stoichiometric amounts of lithium sulfide, boron, and sulfur at 750°C (Li5B7S13) and 700°C (Li9B19S33) with subsequent annealing. The crystal structures consist of interpenetrating, polymeric boron sulfur anion networks which are formed by corner-sharing of B4S10 and B10S20 units (Li5B7S13), or B19S36 units (Li9B19S33). The lithium cations are situated in between with a strong disorder in Li9B19S33.

Li5B7S13 und Li9B19S33: Zwei Lithiumthioborate mit neuen hochpolymeren Anionengerüsten†

For the first time perthioborates with trigonal planar coordination of boron were prepared. Na2B2S5 (Pnma, a = 12.545(2) A, b = 7.441(1) A, c = 8.271(1) A, Z = 4) and Li2B2S5 (Cmcm, a = 15.864(1) A, b = 6.433(1) A, c = 6.862(1) A, Z = 4) were obtained by reaction of the metal sulfides with stoichiometric amounts of boron and an excess of sulfur (effective molar ratio M:B:S = 1:1:4) at 600°C (650°C) and subsequent annealing. The non-isotypic structures contain exactly planar [B2S5]2− groups consisting of five-membered B2S3 rings with one additional exocyclic sulfur on each of the boron atoms. The alkaline metal cations are four-coordinate (lithium) and (four + four)-coordinate (sodium) respectively.



Na2B2S5 und Li2B2S5: Zwei neue Perthioborate mit planaren 1,2,4-Trithia-3,5-Diborolan-Ringen



Na2B2S5 (Pnma, a = 12,545(2) A, b = 7,441(1) A, c = 8,271(1) A, Z = 4) und Li2B2S5 (Cmcm, a = 15,864(1) A, b = 6,433(1) A, c = 6,862(1) A, Z = 4) konnten durch Reaktion der Metallsulfide mit amorphem Bor und elementarem Schwefel im Atomverhaltnis 1:1:4 bei einer Reaktionstemperatur von 600°C (650°C) dargestellt werden. Die Kristallstrukturen bestehen aus planaren, isolierten [B2S5]2−-Funfringen, zwischen denen sich die (vier)- (Lithium) bzw. (vier + vier)-fach (Natrium) koordinierten Kationen befinden.

Na2b2s5 and li2b2s5: two novel perthioborates with planar 1,2,4-trithia-3,5-diborolane rings

Thioborate materials have been considered for novel infrared nonlinear optical (NLO) materials having large optical nonlinear properties combined with favorable laser damage thresholds and wide transmission ranges from the visible to the mid-infrared regions. In this work, known and new thioborate materials have been investigated that have the potential to overcome the low laser damage thresholds of the NLO chalcopyrite sulfide materials such as AgGaS2 without losing their large nonlinear properties and wide transmission ranges. A new thioborate phase, polycrystalline ZnxBa2B2S5+x (x ≈ 0.2), has been prepared by the reaction of the metal sulfides and B2S3 glass in carbon crucibles sealed inside evacuated silica tubes. It crystallizes in the tetragonal system with unit cell parameters of a = 4.762(4) A and c = 24.020(7) A and is based on isolated (BS3)3- structural units. The second harmonic generation (SHG) efficiency determined on powders of ZnxBa2B2S5+x (x ≈ 0.2) is ∼50 times larger than that of α-SiO2....

https://lib.dr.iastate.edu/cgi/viewcontent.cgi?article=1056&context=mse_pubs

Synthesis of the Thioborate Crystal ZnxBa2B2S5+x (x ≈ 0.2) for Second Order Nonlinear Optical Applications

Li4−2xSr2+xB10S19 (x ≈ 0,27) und Na6B10S18 wurden aus der Summenformel entsprechenden Mengen Strontiumsulfid und Lithiumsulfid (Natriumsulfid), amorphem Bor und Schwefel bei 700°C in graphitierten Quarzglasampullen dargestellt. Li4−2xSr2+xB10S19 (x ≈ 0,27) kristallisiert monoklin in der Raumgruppe P21/c mit a = 10,919(2) A, b = 13,590(3) A, c = 16,423(4) A, und β = 90,48(2)°, Na6B10S18 tetragonal in der Raumgruppe I41/acd mit a = 14,415(3) A, c = 26,137(4) A. Beide Strukturen enthalten supertetraedrische B10S20-Einheiten, die uber Tetraederecken zu einem dreidimensionalen polymeren anionischen Raumnetzwerk im Falle des Na6B10S18 bzw. zu eindimensionalen Anionen-Ketten im Falle des Li4−2xSr2+xB10S19 (x ≈ 0,27) verbunden sind. Alle Boratome haben tetraedrische BS4-Koordination (die BS-Abstande variieren von 1,879(5) A bis 1,951(5) A (1,875(10) A bis 1,987(9) A)). Die Strontium- und Lithium-(Natrium-)Kationen befinden sich in ausgedehnten Kanalen innerhalb des Anionengerusts.



Synthesis and Crystal Structures of Li4−2xSr2+xB10S19 (x ≈ 0.27) and Na6B10S18. Two Novel Thioborates with Highly Polymeric Macro-tetrahedral Networks



Li4−2xSr2+xB10S19 (x ≈ 0.27) and Na6B10S18 were prepared from the reaction of strontium sulfide and lithium sulfide (sodium sulfide) with boron and sulfur at 700°C in graphitized silica tubes. Li4−2xSr2+xB10S19 (x ≈ 0.27) crystallizes in the monoclinic space group P21/c with a = 10.919(2) A, b = 13.590(3) A, c = 16.423(4) A, and β = 90.48(2)°, Na6B10S18 in the tetragonal space group I41/acd with a = 14.415(3) A, c = 26.137(4) A. Both structures contain supertetrahedral B10S20 units which are linked through tetrahedral corners to form a three-dimensional polymeric network in the case of Na6B10S18 and one-dimensional chains in the case of Li4−2xSr2+xB10S19 (x ≈ 0.27). All boron atoms are in tetrahedral BS4 coordination (BS bond lengths vary from 1.879(5) to 1.951(5) A (1.875(10) to 1.987(9) A)). The strontium and lithium (sodium) cations are located within large channels formed by the anions.

Darstellung und Kristallstrukturen von Li4−2xSr2+xB10S19 (x ≈ 0,27) und Na6B10S18. Zwei neue Thioborate mit hochpolymeren Makrotetraeder‐Netzwerken

Farblose, plattchenformige Kristalle von RbBS3 (P21/c, a=7,082(2) A, b=11,863(4) A, c=5,794(2) A, β=106,54(2)°) entstehen aus einem stochiometrischen Ansatz von Rubidiumsulfid, Bor und Schwefel bei 600°C und anschliesendem Tempern. Die zu RbBS3 isotype Phase TlBS3 (P21/c, a=6,874(3) A, b=11,739(3) A, c=5,775(2) A, β=113,08(2)°) erhalt man aus dem Ansatz Tl2S · 2 B2S3. Das nach 7 h bei 850°C erhaltene glasige Produkt wird in einem Zweizonenofen 400 h bei 400350°C ausgelagert. Gelbe Kristalle der Verbindung bilden sich in der warmeren Ofenzone. Das ebenfalls gelbe Tl3B3S10 (P1, a=6,828(2) A, b=7,713(2) A, c=13,769(5) A, α=104,32(2)°, β=94,03(3)β, γ=94,69(2)°) bildet sich aus stochiometrischen Mengen von Thalliumsulfid, Bor und Schwefel bei 850°C und anschliesendem Tempern.



Die ausschlieslich tetraedrisch koordiniertes Bor enthaltenden Verbindungen bilden polymere Kettenstrukturen, die sich im Fall des RbBS3 und TlBS3 aus spirocyclisch uber die Boratome verknupften, nichtplanaren Trithiadiborolan-Ringen aufbauen. Ersetzt man in diesen Anionenketten jeden dritten B2S3-Funfring durch einen B(S2)2B-Sechsring, so erhalt man die Anionenstruktur des Tl3B3S10.



The Perthioborates RbBS3, TIBS3, and Tl3B3S10.



RbBS3 (P21/c, a=7.082(2) A, b=11.863(4) A, c=5.794(2) A, β=106.54(2)°) was prepared as colourless, plate-shaped crystals by reaction of stoichiometric amounts of rubidium sulfide, boron, and sulfur at 600°C and subsequent annealing. TlBS3 (P21/c, a=6.874(3) A, b=11.739(3) A, c=5.775(2) A, β=113.08(2)°) which is isotypic with RbBS3 was synthesized from a sample of the composition Tl2S · 2 B2S3. The glassy product which was obtained after 7 h at 850°C was annealed in a two zone furnace for 400 h at 400350°C. Yellow crystals of TlBS3 formed at the warmer side of the furnace.



Tl3B3S10 (P1, a=6.828(2) A, b=7.713(2) A, c=13.769(5) A, α=104.32(2)°, β=94.03(3)°, γ=94.69(2)°) was prepared as yellow plates from stoichiometric amounts of thallium sulfide, boron, and sulfur at 850°C and subsequent annealing.



All compounds contain tetrahedrally coordinated boron. The crystal structures consist of polymeric anion chains. In the case of RbBS3 and TlBS3 nonplanar five-membered B2S3 rings are spirocyclically connected via the boron atoms. To obtain the anionic structure of Tl3B3S10 every third B2S3 ring of the polymeric chains of MBS3 is to be substituted by a six-membered B(S2)2B ring.

C. Püttmann

Papers

Die Perthioborate RbBS3, TIBS3 und TI3B3S10†