Synthesis Of Thiophosphates Research Articles

Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials

AbstractOriented synthesis of functional materials is a focus of attention in material science. As one of the most important function materials, infrared nonlinear optical materials with large second harmonic generation effects and broad optical band gap are in urgent need. In this work, directed by the theoretical structure prediction, the first series of non‐centrosymmetric (NCS) alkali‐alkaline earth metal [PS4]‐based thiophosphates LiCaPS4 (Ama2), NaCaPS4 (P21), KCaPS4 (Pna21), RbCaPS4 (Pna21), CsCaPS4 (Pna21) were successfully synthesized. Comprehensive characterizations reveal that ACaPS4 could be regarded as promising IR NLO materials, exhibiting wide band gap (3.77–3.86 eV), moderate birefringence (0.027–0.064 at 1064 nm), high laser‐induced damage threshold (LIDT, ~10×AGS), and suitable phase‐matching second harmonic generation responses (0.4–0.6×AGS). Structure‐properties analyses illustrate that the Ca−S bonds show non‐ignorable covalent feature, and [PS4] together with [CaSn] units play dominant roles to determine the band gap and SHG response. This work indicates that Li‐, Na‐ and K‐ analogs may be promising infrared nonlinear optical material candidates, and this is the first successful case of “prediction to synthesis” involving infrared (IR) nonlinear optical (NLO) crystals in the thiophosphate system and may provide a new avenue to the design and oriented synthesis of high‐performance function materials in the future.

Structure-Prediction-Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials.

Oriented synthesis of functional materials is a focus of attention in material science. As one of the most important function materials, infrared nonlinear optical materials with large second harmonic generation effects and broad optical band gap are in urgent need. In this work, directed by the theoretical structure prediction, the first series of non-centrosymmetric (NCS) alkali-alkaline earth metal [PS4]-based thiophosphates LiCaPS4 (Ama2), NaCaPS4 (P21), KCaPS4 (Pna21), RbCaPS4 (Pna21), CsCaPS4 (Pna21) were successfully synthesized. Comprehensive characterizations reveal that ACaPS4 could be regarded as promising IR NLO materials, exhibiting wide band gap (3.77-3.86 eV), moderate birefringence (0.027-0.064 at 1064 nm), high laser-induced damage threshold (LIDT, ~10×AGS), and suitable phase-matching second harmonic generation responses (0.4-0.6×AGS). Structure-properties analyses illustrate that the Ca-S bonds show non-ignorable covalent feature, and [PS4] together with [CaSn] units play dominant roles to determine the band gap and SHG response. This work indicates that Li-, Na- and K- analogs may be promising infrared nonlinear optical material candidates, and this is the first successful case of "prediction to synthesis" involving infrared (IR) nonlinear optical (NLO) crystals in the thiophosphate system and may provide a new avenue to the design and oriented synthesis of high-performance function materials in the future.

Trichloroisocyanuric acid-promoted thiolation of phosphites by thiols

A simple and convenient method for the synthesis of thiophosphates by coupling of phosphites with thiols under mild conditions has been developed. The reactions were promoted by trichloroisocyanuric acid (TCCA) and were carried out at room temperature in a one-pot two-step procedure within 20 min. A variety of substrates was tolerated in this method. Notably, both aryl and alkyl thiols could afford the corresponding thiophosphates in good yields.

Synthesis of Thiophosphates by Coupling of Phosphates with Bunte Salts under Mild Conditions

A simple, green, and efficient method has been developed for the preparation of thiophosphates with sodium S-benzyl thiosulfates. The method uses an NaBr-catalyzed coupling reaction of Bunte salts with phosphonates in the presence of an acid and hydrogen peroxide (30%), and the desired products were obtained in good yields.

Synthesis of thiophosphates through a three-component reaction by using sulfur dioxide as the sulfur source

Generation of thiophosphates through a three-component reaction of diaryliodonium tetrafluoroborates, 1,4-diazabicyclo[2.2.2]octane-sulfur dioxide (DABCO·(SO2)2), and diarylphosphine oxides under visible light irradiation is described.

ChemInform Abstract: DCDMH‐Promoted Synthesis of Thiophosphates by Coupling of H‐Phosphonates with Thiols.

AbstractAside the thiophosphates, the corresponding disulfides are often formed as by‐product.

ChemInform Abstract: N‐Chlorosuccinimide‐Promoted Synthesis of Thiophosphates from Thiols and Phosphonates under Mild Conditions.

A very simple N-chlorosuccinimide-promoted synthesis of thiophosphates through the coupling of thiols and phosphonates is reported. Notably, the reactions were carried out in the absence of a base. Functional groups including fluoro, bromo and trifluoromethyl are all tolerated by the reaction conditions employed. Both aryl and alkyl thiols are coupled smoothly with a broad spectrum of phosphonates to afford the corresponding thiophosphates in good to excellent yields.

N-Chlorosuccinimide-promoted synthesis of thiophosphates from thiols and phosphonates under mild conditions

A very simple N-chlorosuccinimide-promoted synthesis of thiophosphates through the coupling of thiols and phosphonates is reported. Notably, the reactions were carried out in the absence of a base. Functional groups including fluoro, bromo and trifluoromethyl are all tolerated by the reaction conditions employed. Both aryl and alkyl thiols are coupled smoothly with a broad spectrum of phosphonates to afford the corresponding thiophosphates in good to excellent yields.