Borate halides are an ideal materials class from which to design high‐performance nonlinear optical (NLO) materials. Currently, borate fluorides, chlorides, and bromides are extensively investigated while borate iodide materials discovery remains rare because of the perceived synthetic challenges. We report a new borate iodide, Pb2BO3I, synthesized by a straightforward hydrothermal method. The Pb2BO3I chemical formula conceals that the compound exhibits a structure similar to the well‐established KBe2BO3F2(KBBF), which we show supports the highest second‐harmonic generation (SHG) at 1064 nm in the KBBF family, 10 × KH2PO4(KDP), arising from the inclusion of Pb2+and I−and the crystal chemistry. Our work shows that KBBF‐related compounds can be synthesized incorporating iodide and exhibit superior NLO responses.
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Joint photoelectron spectroscopy and first-principles theory investigations indicate that the Pb-doped PbB2(BO)
- Award ID(s):
- 2053541
- NSF-PAR ID:
- 10499250
- Publisher / Repository:
- RSC
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 26
- Issue:
- 6
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 5356 to 5367
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
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Abstract Borate halides are an ideal materials class from which to design high‐performance nonlinear optical (NLO) materials. Currently, borate fluorides, chlorides, and bromides are extensively investigated while borate iodide materials discovery remains rare because of the perceived synthetic challenges. We report a new borate iodide, Pb2BO3I, synthesized by a straightforward hydrothermal method. The Pb2BO3I chemical formula conceals that the compound exhibits a structure similar to the well‐established KBe2BO3F2(KBBF), which we show supports the highest second‐harmonic generation (SHG) at 1064 nm in the KBBF family, 10 × KH2PO4(KDP), arising from the inclusion of Pb2+and I−and the crystal chemistry. Our work shows that KBBF‐related compounds can be synthesized incorporating iodide and exhibit superior NLO responses.
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Abstract Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal dπ→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB2O−[Bi≡B−B≡O]−in which both boron atoms can be viewed as sp‐hybridized and the [B−BO]−fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB2O−and ReB2O−and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB2O−has a closed‐shell bent structure (
Cs ,1A ′) with BO−coordinated to an Ir≡B unit, (−OB)Ir≡B, whereas ReB2O−is linear (C ∞v ,3Σ−) with an electron‐precise Re≡B triple bond, [Re≡B−B≡O]−. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems. -
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