Synthesis of Trispirocyclotriphosphazenes with Oxaphosphorine Rings and Their Crystal and Molecular Structures

Abstract

Novel trispirocyclotriphosphazenes with oxaphosphorine rings (DOP-PZs) were successfully synthesized by an Appel reaction with phosphoramide, which was prepared from ammonia and 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, generally abbreviated as DOPO. The resulting DOP-PZs were characterized by 1 H, 13 C{ 1 H}, and 31 P{ 1 H} nuclear magnetic resonance spectroscopy and time-of-flight mass spectrometry and shown to consist of cis−trans isomers. Moreover, the crystal and molecular structures of the DOP-PZs were determined by X-ray diffraction; cis-and trans-DOP-PZs (C 36 H 24 N 3 O 3 P 3 , M = 639.49 g/mol) were refined to final R 1 values of 0.0260 and 0.0463, respectively, with the SHELXL refinement package using least-squares minimization. The crystal of cis-DOP-PZ is trigonal in space group R3c and the following cell constants: a = 19.5984(5) Å, c = 13.2754(4) Å, V = 4415.9(3) Å 3 , Z = 6, and Flack parameter = 0.038(8). In contrast, trans-DOP-PZ is monoclinic in space group P2 1 /c and the following cell constants: a = 9.98647(18) Å, b = 24.1737(4) Å, c = 12.8472(2) Å, β = 112.649(8)°, V = 2862.26(18) Å 3 , and Z = 4. The molecular structures of these DOP-PZs were compared with those of other trispirocyclotriphosphazenes. In addition, the DOP-PZs showed high thermal stability up to 400 °C, with dielectric constants of 2.76−2.77 and dissipation factors of 0.0017−0.0031 at 10 GHz.

Phosphorus-nitrogen compounds: Part 69—Unsymmetrical dispiro(N/N)cyclotriphosphazenes containing different pendant arms: syntheses, characterization, stereogenism, photophysical and bioactivity studies

“…There are fewer articles on the reactions of HCCP with bidentate ligands than with monodentate reagents. Nucleophilic substitution reactions of trimer with bidentate reagents produce compounds of different architectures such as spiro, ansa, bino, dispiro and trispiro [13][14][15][16][17][18][19][20][21][22][23][24]. Considering the reported articles in the scienti c literature, it is also clear that the number of monospirocyclotriphosphazenes is larger than those of dispiro or trispiro compounds.…”

Selective mono substitution of cyclotri-phosphazene by 2-Hydroxyethylacrylate producing new acrylate cyclo-triphosphazene

“…It has been mention, that phosphazene chemistry has brought much attention since 1960 [2] [3]. Especially, hexachlorocyclotriphosphazene (N3 P3 Cl6, trimer) which has a particular interest to both theoretical and experimental researchers concerning phosphazene-based chemistry.…”

Manganese Cyclotriphosphazene Multicarboxylate Frameworks and Composite Encapsulated 1,3,6,8-Tetrakis(p-benzoic acid) Pyrene as Visualization of Highly Selective Fluorescence Sensors for Aromatic Compounds with NH2/NO2 Group

“…Compared with the fluorescent turn-off probe, the fluorescent turn-on probe can be easily identified against a dark background. , Compared with other fluorescent probes, metal–organic framework-based fluorescent probes have received extensive attention owing to their assembly diversity, adjustable pore size, and different fluorescence emission mechanisms. , Compared with rigid poly­(carboxylic acid) ligands, flexible poly­(carboxylic acid) ligands can form a framework with novel topologies and special properties due to their flexibility and conformational diversity. , A wide variety of organic skeletons are easily prepared by the nucleophilic substitution reaction of hexachlorocyclotriphosphazene, and their structure and chemical and physical properties can be easily customized by flexibly selecting the side groups substituted on the phosphorus atom. More importantly, the cyclotriphosphazene and its derivative nitrogen–phosphorus rings are arranged alternately, with six arms on the periphery, and the six arms can be rotated to adjust its configuration. , Therefore, a degree of flexibility is imparted to the entire cyclotriphosphazene skeleton. , Based on the important role of flexible carboxylic acid ligands in the construction of metal–organic frameworks (MOFs) and the easy functionalization of cyclotriphosphazene derivatives, we try to explore building MOF with the multifunctionalization of cyclotriphosphazene carboxylic acid (Scheme S1). However, to our surprise, the fluorescent properties of MOFs with such ligands have still been rarely explored, and their functional development is in its infancy.…”

“…21,22 Therefore, a degree of flexibility is imparted to the entire cyclotriphosphazene skeleton. 23,24 Based on the important role of flexible carboxylic acid ligands in the construction of metal− organic frameworks (MOFs) and the easy functionalization of cyclotriphosphazene derivatives, we try to explore building MOF with the multifunctionalization of cyclotriphosphazene carboxylic acid (Scheme S1). However, to our surprise, the fluorescent properties of MOFs with such ligands have still been rarely explored, and their functional development is in its infancy.…”