Centrosymmetric (NH₄)₂SbCl(SO₄)₂ and Non-centrosymmetric (NH₄)SbCl₂(SO₄): Synergistic Effect of Hydrogen-Bonding Interactions and Lone-Pair Cations on the Framework Structures and Macroscopic Centricities

Abstract

Two new antimony sulfate chlorides named (NH4)2SbCl­(SO4)2 and (NH4)­SbCl2(SO4) were successfully synthesized through solvent-free synthesis method. (NH4)2SbCl­(SO4)2 exhibits a three-dimensional framework constructed of [SbCl­(SO4)2]2– chains and NH4 + ions. And the NH4 + cations play the role of charge balance and provide the hydrogen bond constructed with oxygen atoms. (NH4)­SbCl2(SO4) shows a two-dimensional layer structure that is composed of the regularly stacked [SbCl2(SO4)]− chains via hydrogen-bonding interactions. Both of the titled compounds possess the same chemical composition and the similar Sb–Cl–SO4 chains, while hydrogen-bonding interactions and lone-pair cations play the synergistic effect on the framework structures and macroscopic centricities resulting in that the (NH4)2SbCl­(SO4)2 is centrosymmetric and the (NH4)­SbCl2(SO4) is non-centrosymmetric (NCS). Powder second harmonic generation (SHG) measurements indicated that the NCS compound (NH4)­SbCl2(SO4) is type I phase-matchable and exhibits SHG responses of ∼1.7 times that of KH2PO4.

A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component Design

“…Recently, (NH 4 )SbCl 2 (SO 4 ) was reported having a moderate SHG response (1.7×KDP), and the cooperation of SbCl 2 O 2 and SO 4 polyhedrons makes a major contribution to the SHG effect. However, it is still unstable in the heating process (weight loss begins at 163 °C) and susceptive to humidity …”

Simulation Meets Experiment: Unraveling the Properties of Water in Metal–Organic Frameworks through Vibrational Spectroscopy

“…Hydrogen bonding (H-bonding) between water and host materials has proven to be important for the structure and function of the latter. − Strong H-bonds can lead to the formation of extended networks that modulate fundamental processes, including hydration processes, chemical synthesis and reactions, , heat dissipation, , and macroscopic structural formations. ,− Under confinement, H-bonded networks are disrupted due to physical constraints and host–water interactions. , A variety of porous materials, such as carbon nanotubes, − zeolites, silica pores and channels, , and other materials , have been used as model systems to determine the physical properties of water in confinement. These model systems highlight the fact that the properties of the confining environment, whether hydrophobic or hydrophilic, influence H-bonding with the host.…”

K2Sb(P2O7)F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance

“…K 2 Sb(P 2 O 7 )F displays a strong SHG response of about 4.0 times larger than that of KH 2 PO 4 (KDP), which is nearly 3.0 times that of KBBF. With the exception of a few lead phosphates and LiHgPO 4 , [27] this value is much larger than that of most of the emerging UV NLO phosphates, especially, pyrophosphates, e.g., Rb 2 Ba 3 (P 2 O 7 ) 2 (0.3×KDP), [28] RbNaMgP 2 O 7 (0.9×KDP), [29] K 4 Mg 4 (P 2 O 7 ) 3 (1.3×KDP) [22] etc., as well as antimony(III)‐based NLO materials such as K 2 SbF 3 SO 4 (0.1×KDP), [18c] Rb 2 Sb 2 F 6 SO 4 (0.3×KDP), [18d] (NH 4 )SbSO 4 Cl 2 (1.7×KDP) [18b] and CsSbF 2 SO 4 (3.0×KDP) [18a] …”